Xanthene dye

ABSTRACT

A colored composition of the present invention includes a dye compound having an anionic moiety including at least one of a structure represented by the following General Formula (A1), a structure represented by the following General Formula (A2), and a structure containing a boron atom, and a dye structure having a cationic moiety, in which the anionic moiety and the cationic moiety are bonded to each other via a covalent bond and present in the same molecule; a curable compound; and a solvent. 
     
       
         
         
             
             
         
       
         
         
           
             (in General Formula (A1), R 1  and R 2  each independently represent —SO 2 — or —CO—) 
           
         
       
    
     
       
         
         
             
             
         
       
         
         
           
             (in General Formula (A2), R 3  represents —SO 2 — or —CO—; and R 4  and R 5  each independently represent —SO 2 —, —CO—, or —CN)

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Divisional Application of U.S. application Ser.No. 15/014,756 filed on Feb. 3, 2016, which is a Continuation of PCTInternational Application No. PCT/JP2014/072213 filed on Aug. 26, 2014,which claims priority under 35 U.S.C § 119(a) to Japanese PatentApplication No. 2013-185377 filed on Sep. 6, 2013 and Japanese PatentApplication No. 2014-165546 filed on Aug. 15, 2014. Each of the aboveapplications is hereby expressly incorporated by reference, in itsentirety, into the present application.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to a colored composition and a cured filmusing the same. The present invention further relates to a color filterhaving a cured film, a method for manufacturing a color filter, and asolid-state imaging element and an image display device, each of whichhas the color filter. In addition, the present invention relates to apolymer and a xanthene dye.

2. Description of the Related Art

As one of the methods for manufacturing a color filter which is used fora liquid crystal display device, a solid-state imaging element, or thelike, there is a pigment dispersion method. As the pigment dispersionmethod, there is a method for manufacturing a color filter byphotolithography using a coloring photosensitive composition which isobtained by dispersing pigments in various photosensitive compositions.That is, a colored photosensitive composition is applied onto asubstrate by using a spin coater, a roll coater, or the like, thecolored photosensitive composition is dried to form a coating film, andthe coating film is patternwise exposed and developed, thereby obtainingcolored pixels. This operation is repeated for the number of the desiredhues to manufacture a color filter.

The color filter obtained by the above method is stable with respect tolight or heat due to a use of pigments, and positional accuracy of thecolored pixels is sufficiently secured since patterning is performed byphotolithography. Accordingly, the method has been widely used as amethod suitable for manufacturing a color filter for color display orthe like.

However, it is common to use a colored composition including a dye or apigment for the manufacture of a color filter. For example,JP1994-503842A (JP-H06-503842A) discloses abis(perfluorosulfonyl)methane derivative. JP2012-107192A,JP2012-108469A, WO2013/011687A, and WO2011/158748A each disclose acomposition including a compound having a counter salt type xanthenestructure as a colorant.

SUMMARY OF THE INVENTION

The present inventors have conducted investigations and as a result, itwas found that when a color filter is formed using the compounddescribed in JP2012-107192A, JP2012-108469A, WO2013/011687A, orWO2011/158748A, the color filter tends to have deterioration in heatresistance.

The present invention has been made to solve the above-describedproblem, and accordingly, has an object to provide a colored compositionwhich is capable of providing a color filter having excellent heatresistance, and another object to provide a polymer and a xanthene dye.

After the present inventors have conducted extensive investigations, itcould be seen that the compound described in JP2012-107192A,JP2012-108469A, WO2013/011687A. or WO2011/158748A is formed of a dyecompound having a weakly nucleophilic anion as a counter anion, andtherefore, it has deterioration in heat resistance. That is, it wasfound that for a dye compound having a weakly nucleophilic anion as acounter anion, the counter anion is salt-exchanged with another anion,which causes deterioration in heat resistance. In addition, the presentinventors have found out that by adopting a compound having apredetermined weakly nucleophilic anionic moiety and a predeterminedcationic moiety in the same molecule as a dye compound, theabove-described problems can be solved.

Specifically, the problems were solved by the following means <1>, andpreferably by <2> to <21>.

<1> A colored composition including:

a dye compound having

-   -   a dye structure having a cationic moiety and    -   an anionic moiety including at least one of a structure        represented by the following General Formula (A1), a structure        represented by the following General Formula (A2), and a        structure containing a boron atom,    -   in which the anionic moiety and the cationic moiety are bonded        to each other via a covalent bond and present in the same        molecule:

a curable compound; and

a solvent.

(in General Formula (A1), R¹ and R² each independently represent —SO₂—or —CO—)

(in General Formula (A2), R³ represents —SO₂— or —CO—; and R⁴ and R⁵each independently represent —SO₂—, —CO—, or —CN)

<2> The colored composition as described in <1>, in which the dyestructure having a cationic moiety has a dye structure selected from axanthene dye, a cyanine dye, a squarylium dye, and a dipyrromethene dye.

<3> The colored composition as described in <1>, in which the dyestructure having a cationic moiety is a xanthene structure.

<4> The colored composition as described in any one of <1> to <3>,having a structure in which at least any one of a fluorine atom, analiphatic hydrocarbon group containing a fluorine atom, an aromatichydrocarbon group containing a fluorine atom, an aromatic hydrocarbongroup containing a nitro group, and an aromatic hydrocarbon groupcontaining a cyano group is bonded to at least one of R¹ to R⁵ in thestructure represented by General Formula (A1) or General Formula (A2)via a covalent bond.

<5> The colored composition as described in any one of <1> to <4>, inwhich the anionic moiety has a structure represented by the followingGeneral Formula (A3-1) or (A3-2).

(in General Formula (A3-1), L¹ represents —SO₂— or —CO—; G represents acarbon atom or a nitrogen atom; n1 represents 2 in the case where G is acarbon atom and represents 1 in the case where G is a nitrogen atom; R⁶represents an alkyl group containing a fluorine atom, an aryl groupcontaining a fluorine atom, an aryl group containing a nitro group, oran aryl group containing a cyano group; in the case where n1 is 2, twoR⁶'s may be the same as or different from each other; and * represents asite bonding to another site)

(in General Formula (A3-2), L represents —SO₂— or —CO—; represents acarbon atom or a nitrogen atom; n1 represents 2 in the case where G is acarbon atom and represents 1 in the case where G is a nitrogen atom; R⁷represents an alkylene group containing a fluorine atom, an arylenegroup containing a fluorine atom, an arylene group containing a nitrogroup, or an arylene group containing a cyano group; * represents a sitebonding to another site; and in the case where n1 is 2, two R⁷'s may bethe same as or different from each other)

<6> The colored composition as described in any one of <1> to <5>, inwhich the dye compound is a dye multimer having two or more dyestructures having a cationic moiety in the molecule.

<7> The colored composition as described in <6>, in which the dyecompound is a polymer having a repeating unit represented by GeneralFormula (A4-1) and/or General Formula (A4-3).

(in General Formula (A4-1), one of R¹⁰ to R¹⁴ is a repeating unitrepresented by the following General Formula (A4-1-2), at least one ofR¹⁰ to R¹⁴ is a group represented by the following General Formula(A4-1-1), and the remainders of R¹⁰ to R¹⁴ each independently representa hydrogen atom, an aliphatic hydrocarbon group, or an aromatichydrocarbon group)

(in General Formula (A4-1-1), L¹ represents a single bond or a divalentlinking group; L² represents —SO₂— or —CO—; G represents a carbon atomor a nitrogen atom; n1 represents 2 in the case where G is a carbon atomand represents 1 in the case where G is a nitrogen atom; R⁶ representsan alkyl group containing a fluorine atom or an aryl group containing afluorine atom; and in the case where n is 2, two R⁶'s may be the same asor different from each other)

(in General Formula (A4-1-2), L¹¹ represents a single bond or a divalentlinking group; and R^(X) represents a hydrogen atom, a methyl group, ahydroxymethyl group, or an alkoxymethyl group)

(in General Formula (A4-3), four of R¹⁰ to R¹⁴ each independentlyrepresent a hydrogen atom, an aliphatic hydrocarbon group, or anaromatic hydrocarbon group, and one of R¹⁰ to R¹⁴ is a repeating unitrepresented by the following General Formula (A4-3-1))

(in General Formula (A4-3-1), L¹ represents a single bond or a divalentlinking group; L² represents —SO₂— or —CO—; L³ represents a divalentlinking group; G represents a carbon atom or a nitrogen atom; in thecase where G is a carbon atom, n2 represents 1, and in the case where Grepresents a nitrogen atom, n2 represents 0; R^(7A) and R^(7B) eachindependently represent an alkylene group containing a fluorine atom oran arylene group containing a fluorine atom; and R^(X) represents ahydrogen atom, a methyl group, a hydroxymethyl group, or an alkoxymethylgroup)

<8> The colored composition as described in <7>, in which the dyecompound is a polymer having the repeating unit represented by GeneralFormula (A4-3).

<9> The colored composition as described in any one of <1> to <8>, inwhich the dye compound has a polymerizable group.

<10> The colored composition as described in any one of <1> to <8>, inwhich the dye compound has an alkali-soluble group.

<11> The colored composition as described in any one of <1> to <10>,further including a photopolymerization initiator.

<12> The colored composition as described in any one of <1> to <11>,further including a pigment having a phthalocyanine skeleton.

<13> The colored composition as described in any one of <1> to <12>,used for formation of a colored layer of a color filter.

<14> A cured film obtained by curing the colored composition asdescribed in any one of <1> to <12>.

<15> A color filter including the cured film as described in <14>.

<16> A method for manufacturing a color filter, including a step ofapplying the colored composition as described in any one of <1> to <13>onto a support to form a colored composition layer, a step ofpatternwise exposing the colored composition layer, and a step ofdeveloping an unexposed area of the exposed colored composition layer.

<17> A method for manufacturing a color filter, including:

a step of applying the colored composition as described in any one of<1> to <13> onto a support to form a colored composition layer andcuring the colored composition layer to form a colored layer,

a step of forming a photoresist layer on the colored layer,

a step of patterning the photoresist layer by exposure and developmentto obtain a resist pattern, and

a step of dry-etching the colored layer using the resist pattern as anetching mask.

<18> A solid-state imaging element including the color filter asdescribed in <15> or a color filter manufactured by the method formanufacturing a color filter as described in <16> or <17>.

<19> An image display device including the color filter as described in<15> or a color filter manufactured by the method for manufacturing acolor filter as described in <16> or <17>.

<20> A polymer having a repeating unit represented by General Formula(A4-1) and/or General Formula (A4-3).

(in General Formula (A4-1), one of R¹⁰ to R¹⁴ is a repeating unitrepresented by the following General Formula (A4-1-2), at least one ofR¹⁰ to R¹⁴ is a group represented by the following General Formula(A4-1-1), and the remainders of R¹⁰ to R¹⁴ each independently representa hydrogen atom, an aliphatic hydrocarbon group, or an aromatichydrocarbon group)

(in General Formula (A4-1-1), L¹ represents a single bond or a divalentlinking group; L² represents —SO₂— or —CO—; G represents a carbon atomor a nitrogen atom; and n1 represents 2 in the case where G is a carbonatom and represents 1 in the case where G is a nitrogen atom. R⁶represents an alkyl group containing a fluorine atom or an aryl groupcontaining a fluorine atom; and in the case where n1 is 2, two R⁶'s maybe the same as or different from each other)

(in General Formula (A4-1-2), L¹¹ represents a single bond or a divalentlinking group; and R^(X) represents a hydrogen atom, a methyl group, ahydroxymethyl group, or an alkoxymethyl group)

(in General Formula (A4-3), four of R¹⁰ to R¹⁴ each independentlyrepresent a hydrogen atom, an aliphatic hydrocarbon group, or anaromatic hydrocarbon group, and one of R¹⁰ to R¹⁴ is a repeating unitrepresented by the following General Formula (A4-3-1))

(in General Formula (A4-3-1), L¹ represents a single bond or a divalentlinking group; L² represents —SO₂— or —CO—; L³ represents a divalentlinking group; G represents a carbon atom or a nitrogen atom; in thecase where G is a carbon atom, n2 represents 1, and in the case where Grepresents a nitrogen atom, n2 represents 0; R^(7A) and R^(7B) eachindependently represent an alkylene group containing a fluorine atom oran arylene group containing a fluorine atom; and R^(X) represents ahydrogen atom, a methyl group, a hydroxymethyl group, or an alkoxymethylgroup)

<21> A xanthene dye represented by General Formula (A5).

(in General Formula (A5), R²⁰ to R²³ each independently represent ahydrogen atom, an aliphatic hydrocarbon group, or an aromatichydrocarbon group; and A represents an anionic moiety represented by anyone of the following General Formula (AN-1) to (AN-4))

(in General Formula (AN-1), * represents a bonding site to a xanthenestructure; and Rf₁ represents an aliphatic hydrocarbon group, ahalogenated aliphatic hydrocarbon group, an aromatic hydrocarbon group,or a halogenated aromatic hydrocarbon group;

-   -   in General Formula (AN-2), * represents a bonding site to a        xanthene structure; and Rf₂ represents a halogenated aliphatic        hydrocarbon group;    -   in General Formula (AN-3), * represents a bonding site to a        xanthene structure; Rf₃ represents an aliphatic hydrocarbon        group, a halogenated aliphatic hydrocarbon group, an aromatic        hydrocarbon group, or a halogenated aromatic hydrocarbon group;        and B represents a substituent; and

in General Formula (AN-4), * represents a bonding site to a xanthenestructure; Rf₄ represents a halogenated aliphatic hydrocarbon group; andB represents a substituent)

According to the present invention, it became possible to provide acolored composition having excellent heat resistance.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a view showing the ¹H-NMR spectrum of a xanthene dye compound(P-1).

FIG. 2 is a view showing the ¹H-NMR spectrum of a xanthene dye compound(P-25).

FIG. 3 is a view showing the ¹H-NMR spectrum of a xanthene dye compound(P-29).

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hereinafter, the contents of the present invention will be described indetail. Further, in the present specification, “(a value) to (a value)”is used to mean a range including the numeral values described beforeand after are included as a lower limit value and an upper limit value,respectively. Further, the organic EL element in the present inventionrefers to an organic electroluminescence element.

In the specification, the total solid content refers to a total mass ofthe components of the entire composition of a colored compositionexcluding a solvent.

In citations for a group (atomic group) in the present specification,when the group is denoted without specifying whether it is substitutedor unsubstituted, the group includes both a group having no substituentand a group having a substituent. For example, an “alkyl group” includesnot only an alkyl group having no substituent (unsubstituted alkylgroup), but also an alkyl group having a substituent (substituted alkylgroup).

Furthermore, “radiation” in the present specification means, forexample, a bright line spectrum of a mercury lamp, far ultraviolet raysrepresented by an excimer laser, extreme ultraviolet rays (EUV rays),X-rays, electron beams, or the like. In addition, in the presentinvention, light means actinic rays or radiation. “Exposure” in thepresent specification includes, unless otherwise specified, not onlyexposure by a mercury lamp, far ultraviolet rays represented by anexcimer laser, X-rays. EUV rays, or the like, but also writing byparticle rays such as electron beams and ion beams.

Furthermore, in the present specification, “(meth)acrylate” representseither or both of an acrylate and a methacrylate. “(meth)acryl”represents either or both of an acryl and a methacryl, and“(meth)acryloyl” represents either or both of an acryloyl and amethacryloyl.

In addition, in the present specification, a “monomer material” and a“monomer” have the same definition. The monomer in the presentspecification refers to a compound which is distinguished from anoligomer or a polymer and has a weight-average molecular weight of 2,000or less. In the present specification, a polymerizable compound refersto a compound having a polymerizable functional group, and may be amonomer or a polymer. The polymerizable functional group refers to agroup involved in a polymerization reaction.

In the present specification, in the formulae, Me represents a methylgroup, Et represents an ethyl group, Pr represents a propyl group. Burepresents a butyl group, and Ph represents a phenyl group.

In the present specification, a term “step” includes not only anindependent step, but also steps which are not clearly distinguishedfrom other steps if an intended action of the steps is obtained.

The colored composition of the present invention (hereinafter simplyreferred to as “the composition of the present invention” in some cases)may include a dye compound (A) having an anionic moiety including atleast one of a structure represented by the following General Formula(A1), a structure represented by the following General Formula (A2), anda structure containing a boron atom, and a cationic moiety, in which theanionic moiety and the cationic moiety are bonded to each other via acovalent bond and present in the same molecule.

a curable compound (B), and

a solvent (C).

By adopting such a configuration, it is possible to provide a coloredcomposition having excellent heat resistance. Further, the solubility ina solvent can also be improved. In addition, when forming a coloredpattern, color migration properties can be improved and a change inspectrum between before and after the development can be inhibited.

The expression of the anionic moiety and the cationic moiety beingbonded to each other via a covalent bond means that the anionic moietymay be directly bonded to a dye structure having a cationic moiety; theanionic moiety and the cationic moiety are linked via a linking group;or the bonds in these linking groups may all be covalent bonds.

<Dye Compound (A)>

The dye compound (A) which is used in the present invention has ananionic moiety including at least one of a structure represented by thefollowing General Formula (A1), a structure represented by the followingGeneral Formula (A2), and a structure containing a boron atom, and a dyestructure having a cationic moiety, in which the anionic moiety and thecationic moiety are bonded to each other via a covalent bond and presentin the same molecule. It is preferable that the dye compound (A)includes an anionic moiety including a structure represented by thefollowing General Formula (A1) and/or (A2).

The dye compound in the present invention is one which is referred to aso-called betaine structure, and it may include an anion structurehaving a counter cation or a cationic structure having a counter anionin the molecule within a range where there is no deviation from the gistof the present invention.

(In General Formula (A1), R¹ and R² each independently represent —SO₂—or —CO—.)

(In General Formula (A2), R³ represents —SO₂— or —CO—. R⁴ and R⁵ eachindependently represent —SO₂—, —CO—, or —CN.)

In General Formula (A1), R¹ and R² each independently represent —SO₂— or—CO—, it is preferable that at least one of R¹ and R² represents —SO₂—,and it is more preferable that both of R¹ and R² represent —SO₂—.

In General Formula (A2), R³ represents —SO₂— or —CO—, and R⁴ and R⁵ eachindependently represent —SO₂—, —CO—, or —CN. It is preferable that atleast one of R³ to R⁵ represents —SO₂—, and it is more preferable thatat least two of R³ to R⁵ represent —SO₂—. It is particularly preferablethat all of R³ to R⁵ represent —SO₂—; R³ and R⁵ represent —SO₂— and R⁴represents —CO—; or R⁴ and R⁵ represent —SO₂— and R³ represents —CO—.

For the dye compound (A) which is used in the present invention, it ispreferable that at least any one of a fluorine atom, an aliphatichydrocarbon group containing a fluorine atom, an aromatic hydrocarbongroup containing a fluorine atom, an aromatic hydrocarbon groupcontaining a nitro group, and an aromatic hydrocarbon group containing acyano group is directly bonded to at least one of R¹ to R⁵ in thestructure represented by General Formula (A1) or General Formula (A2)via a covalent bond.

This mechanism is presumed as follows: by adopting such a configuration,since the anionic moiety can be shielded by a more steric or hydrophobiceffect, the intermolecular antistatic electric interactions can furtherbe inhibited, and as a result, the solvent solubility can further beimproved.

The aliphatic hydrocarbon group containing a fluorine atom is preferablyan alkyl group containing a fluorine atom or an alkylene groupcontaining a fluorine atom. The number of carbon atoms of the aliphatichydrocarbon group containing a fluorine atom is preferably 1 to 6, morepreferably 1 to 4, and still more preferably 1 to 3. Further, thealiphatic hydrocarbon group containing a fluorine atom may be linear,branched, or cyclic, but is more preferably linear.

The aromatic hydrocarbon group containing a fluorine atom is preferablyan aryl group containing a fluorine atom or an arylene group containinga fluorine atom. The number of carbon atoms of the aromatic hydrocarbongroup containing a fluorine atom is preferably 6 to 18, more preferably6 to 12, and still more preferably 6.

The aromatic hydrocarbon group containing a fluorine atom preferably hasa content of fluorine atoms of 50% or more, and is more preferably aperfluoro group. The content of fluorine atoms is shown as below.

Content of fluorine atoms=[(atomic weight of fluorine)×(number offluorine atoms)/(molecular weight of the aliphatic hydrocarbon groupcontaining a fluorine atom or the aromatic hydrocarbon group containinga fluorine atom)]×100

The aromatic hydrocarbon group containing a nitro group is preferably anaryl group containing a nitro group or an arylene group containing anitro group. The number of carbon atoms of the aromatic hydrocarbongroup is preferably 6 to 18, more preferably 6 to 12, and still morepreferably 6.

The aromatic hydrocarbon group containing a cyano group is preferably anaryl group containing a nitro group or an arylene group containing acyano group. The number of carbon atoms of the aromatic hydrocarbongroup is preferably 6 to 18, more preferably 6 to 12, and still morepreferably 6.

For the dye compound (A) which is used in the present invention, it ispreferable that the anionic moiety has a structure represented by thefollowing General Formula (A3-1) or (A3-2).

(In General Formula (A3-1), L¹ represents —SO₂— or —CO—. G represents acarbon atom or a nitrogen atom. n1 represents 2 in the case where G is acarbon atom and represents 1 in the case where G is a nitrogen atom. R⁶represents an alkyl group containing a fluorine atom, an aryl groupcontaining a fluorine atom, an aryl group containing a nitro group, oran aryl group containing a cyano group. In the case where n is 2, twoR⁶'s may be the same as or different from each other. * represents asite bonding to another site.)

(In General Formula (A3-2), L¹ represents —SO₂— or —CO—. G represents acarbon atom or a nitrogen atom. n1 represents 2 in the case where G is acarbon atom and represents 1 in the case where G is a nitrogen atom. R⁷represents an alkylene group containing a fluorine atom, an arylenegroup containing a fluorine atom, an arylene group containing a nitrogroup, or an arylene group containing a cyano group. * represents a sitebonding to another site. In the case where n1 is 2, two R⁷'s may be thesame as or different from each other.)

In General Formula (A3-1), R⁶ represents an alkyl group containing afluorine atom or an aryl group containing a fluorine atom, has the samedefinition as the aforementioned alkyl group containing a fluorine atomor an aryl group containing a fluorine atom, and is preferably aperfluoromethyl group.

In General Formula (A3-1), * represents a site bonding to another site.Here, another site represents a site other than the structurerepresented by General Formula (A3-1) in the dye compound (A). The bondbetween * in General Formula (A3-1) and another site is a covalent bond.

In General Formula (A3-2), R⁷ represents an alkylene group containing afluorine atom, an arylene group containing a fluorine atom, an arylenegroup containing a nitro group or an arylene group containing a cyanogroup, has the same definition as the aforementioned alkylene groupcontaining a fluorine atom, arylene group containing a fluorine atom,arylene group containing a nitro group, or arylene group containing acyano group, and is preferably an alkylene group containing a fluorineatom or an arylene group containing a fluorine atom, and more preferablya perfluoroalkylene group having 1 to 3 carbon atoms or aperfluoroarylene group having 6 to 12 carbon atoms.

In General Formula (A3-2), * represents a site bonding to another siteand has the same definition as * in General Formula (A3-1).

<Dye Structure>

The dye structure having a cationic moiety, that is, a partial structure(hereinafter also referred to as a “dye structure”) derived from a dyein the dye (A), is not particularly limited as long as it has a cationin the molecule, and various dye residues having known dye structurescan be applied. Specific examples of the known dye structure include dyestructures derived from a dye selected from a dipyrromethene dye, acarbonium dye (a diphenylmethane dye, a xanthene dye, an acridine dye,and the like), a polymethine dye (an oxonol dye, a merocyanine dye, anarylidene dye, a styryl dye, a cyanine dye, a squarylium dye, acroconium dye, and the like), a subphthalocyanine dye, and metal complexdyes of these.

Among these dye structures, from the viewpoint of color characteristics,dye structures derived from a dye selected from a dipyrromethene dye, acarbonium dye, and a polymethine dye are preferable, dye structuresderived from a dye selected from a xanthene dye, a cyanine dye, asquarylium dye, and a dipyrromethene dye are preferable, and dyestructures derived from a xanthene dye are particularly preferable.

<<Xanthene Dye>>

The dye structure derived from a xanthene dye is preferably representedby the following General Formula (J).

(In General Formula (J), R⁸¹, R⁸², R⁸³, and R⁸⁴ each independentlyrepresent a hydrogen atom or a monovalent substituent. R⁸⁵'s eachindependently represent a monovalent substituent, and m represents aninteger of 0 to 5.)

In General Formula (J), R⁸¹ and R⁸², R⁸³ and R⁸⁴ and R⁸⁵'s in the casewhere m is 2 or more may be each independently bonded to each other toform a 5-, 6-, or 7-membered saturated ring or a 5-, 6-, or 7-memberedunsaturated ring. In the case where the formed 5-, 6-, or 7-memberedring is a group which can be further substituted, the ring may besubstituted with the substituents described for R⁸¹ to R⁸⁵. In the casewhere the ring is substituted with two or more substituents, thesesubstituents may be the same as or different from each other.

In General Formula (J), in the case where R⁸¹ and R⁸², R⁸³ and R⁸⁴, andR⁸⁵'s in the case where m is 2 or more are each independently bonded toeach other to form 5-, 6-, and 7-membered saturated rings not having asubstituent or form 5-, 6-, and 7-membered unsaturated rings, examplesof the 5-, 6-, and 7-membered saturated rings not having a substituentor the 5-, 6-, and 7-membered unsaturated rings include a pyrrole ring,a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, atriazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, apiperidine ring, a cyclopentene ring, a cyclohexene ring, a benzenering, a pyridine ring, a pyrazine ring, and a pyridazine ring, andpreferably a benzene ring and a pyridine ring.

Examples of the substituent which R⁸¹ to R⁸⁴ and R⁸⁵ in General Formula(J) may have include the substituent group A which will be describedlater.

In the dye structure, the cation is not localized, and thus, it ispresent on a nitrogen atom or a carbon atom of a xanthene ring, forexample, as shown below.

The compounds having xanthene skeletons represented by General Formula(J) may be synthesized using methods disclosed in literature.Specifically, the methods disclosed in Tetrahedron Letters, 2003, vol.44, No. 23, pp. 4355 to 4360; Tetrahedron, 2005, vol. 61, No. 12, pp.3097 to 3106; and the like can be applied.

Examples of the dye structure of the xanthene compounds are shown below,but the present invention is not limited thereto.

TABLE 1

No. R¹ R² R³ R⁴ (XT-1) Me Me Me Me (XT-2) Et Et Et Et (XT-3) n-Pr n-Prn-Pr n-Pr (XT-4) i-Pr i-Pr i-Pr i-Pr (XT-5) n-Bu n-Bu n-Bu n-Bu (XT-6)sec-Bu sec-Bu sec-Bu sec-Bu (XT-7) i-Bu i-Bu i-Bu i-Bu (XT-8) tert-Butert-Bu tert-Bu tert-Bu (XT-9) n-C₆H₁₃ n-C₆H₁₃ n-C₆H₁₃ n-C₆H₁₃ (XT-10)n-C₁₈H₃₇ n-C₁₈H₃₇ n-C₁₈H₃₇ n-C₁₈H₃₇ (XT-11) Me Et Me Et (XT-12)—CH₂CH₂OCH₂CH₂— —CH₂CH₂OCH₂CH₂— (XT-13) —(CH₂)₅— —(CH₂)₅— (XT-14)—(CH₂)₄— —(CH₂)₄— (XT-15) —(CH₂)₅— —(CH₂)₄— (XT-16) CH₂Ph CH₂Ph CH₂PhCH₂Ph (XT-17) Et CH₂CH₂OMe Et CH₂CH₂OMe (XT-18) Me cyclo-C 

H₁₁ Me cyclo-C 

H₁₁ (XT-19) CH₂C≡CH CH₂C≡CH CH₂C≡CH CH₂C≡CH (XT-20) CH₂CH═CH₂ CH₂CH═CH₂CH₂CH═CH₂ CH₂CH═CH₂ (XT-21) Me H Me H (XT-22) Et H Et H (XT-23) n-Pr Hn-Pr H (XT-24) i-Pr H i-Pr H (XT-25) n-Bu H n-Bu H (XT-26) H H H H(XT-27) i-Bu H i-Bu H (XT-28) tert-Bu H tert-Bu H (XT-29) n-C₆H₁₃ Hn-C₆H₁₃ H (XT-30) n-C₁₈H₃₇ H n-C₁₈H₃₇ H (XT-31) Ph H Ph H (XT-32) CH₂PhH CH₂Ph H (XT-33) cyclo-C 

H₁₁ H cyclo-C 

H₁₁ H (XT-34) cyclo-C 

H 

H cyclo-C 

H 

H (XT-35) CH₂C≡CH H CH₂C≡CH H (XT-36) CH₂CH═CH₂ H CH₂CH═CH₂ H (XT-37)

H

H (XT-38)

H

H

indicates data missing or illegible when filed

TABLE 2

No. R¹ R² R³ R⁴ (XT-39) Me Me Me Me (XT-40) Et Et Et Et (XT-41) n-Prn-Pr n-Pr n-Pr (XT-42) i-Pr i-Pr i-Pr i-Pr (XT-43) n-Bu n-Bu n-Bu n-Bu(XT-44) sec-Bu sec-Bu sec-Bu sec-Bu (XT-45) i-Bu i-Bu i-Bu i-Bu (XT-46)tert-Bu tert-Bu tert-Bu tert-Bu (XT-47) n-C₆H₁₃ n-C₆H₁₃ n-C₆H₁₃ n-C₆H₁₃(XT-48) n-C₁₈H₃₇ n-C₁₈H₃₇ n-C₁₈H₃₇ n-C₁₈H₃₇ (XT-49) Me Et Me Et (XT-50)—CH₂CH₂OCH₂CH₂— —CH₂CH₂OCH₂CH₂— (XT-51) —(CH₂)₅— —(CH₂)₅— (XT-52)—(CH₂)₄— —(CH₂)₄— (XT-53) —(CH₂)₅— —(CH₂)₄— (XT-54) CH₂Ph CH₂Ph CH₂PhCH₂Ph (XT-55) Et CH₂CH₂OMe Et CH₂CH₂OMe (XT-56) Me cyclo-C 

H₁₁ Me cyclo-C 

H₁₁ (XT-57) CH₂C≡CH CH₂C≡CH CH₂C≡CH CH₂C≡CH (XT-58) CH₂CH═CH₂ CH₂CH═CH₂CH₂CH═CH₂ CH₂CH═CH₂ (XT-59) Me H Me H (XT-60) Et H Et H (XT-61) n-Pr Hn-Pr H (XT-62) i-Pr H i-Pr H (XT-63) H H H H (XT-64) sec-Bu H sec-Bu H(XT-65) i-Bu H i-Bu H (XT-66) tert-Bu H tert-Bu H (XT-67) n-C₆H₁₃ Hn-C₆H₁₃ H (XT-68) n-C₁₈H₃₇ H n-C₁₈H₃₇ H (XT-69) Ph H Ph H (XT-70) CH₂PhH CH₂Ph H (XT-71) cyclo-C 

H₁₁ H cyclo-C 

H₁₁ H (XT-72) cyclo-C 

H 

H cyclo-C 

H 

H (XT-73) CH₂C≡CH H CH₂C≡CH H (XT-74) CH₂CH═CH₂ H CH₂CH═CH₂ H (XT-75)

H

H (XT-76)

H

H

indicates data missing or illegible when filed

The dye compound (A) which is used in the colored composition of thepresent invention may be a dye monomer having one dye structure(hereinafter also referred to as a monomeric xanthene compound) having acationic moiety as described above in the molecule or may be dyemultimer (hereinafter also referred to as a polymeric xanthene compound)having two or more dye structures having a cationic moiety in themolecule. In particular, the dye compound (A) is preferably a dyemultimer.

<Monomeric Xanthene Compound>

The monomeric xanthene compound which is used in the present inventionpreferably contains a polymerizable group.

By adopting such a configuration, the heat resistance tends to beimproved. One kind or two or more kinds of polymerizable group may becontained.

As the polymerizable group, known polymerizable groups which can becrosslinked by a radical, an acid, or heat can be used, and examplesthereof include a group having an ethylenically unsaturated bond, acyclic ether group (an epoxy group or an oxetane group), and a methylolgroup. In particular, a group having an ethylenically unsaturated bondis preferable, and a (meth)acryloyl group is more preferable.

The number of the polymerizable group in one molecule of the monomericxanthene compound is preferably 1 to 4, and more preferably 1 or 2.

The monomeric xanthene compound may contain an acid group. Examples ofthe acid group include a carboxylic acid group, a sulfonic acid group,and a phosphoric acid group.

Furthermore, the monomeric xanthene compound may have an alkali-solublegroup. Examples of the alkali-soluble group include a phenolic hydroxylgroup and a carboxylic acid group. Examples of a method for introducingthe alkali-soluble group into the monomeric xanthene compound include amethod in which an alkali-soluble group is introduced in advance intothe monomeric xanthene compound.

The number of acid groups of the monomeric xanthene compound ispreferably 1 to 4, and more preferably 1 or 2.

In addition, examples of the functional group which the monomericxanthene compound may have include a development accelerator such aslactone, acid anhydride, amide, —COCH₂CO—, and a cyano group, ahydrophobicity-adjusting group such as an aralkyl group, an aryl group,a polyalkylene oxide group, a hydroxyl group, a maleimide group, and anamino group, which can be appropriately introduced.

The acid value of the monomeric xanthene compound which is used in thepresent invention is preferably 5 mgKOH/g to 200 mgKOH/g, and morepreferably 10 mgKOH/g to 180 mgKOH/g.

The monomeric xanthene compound (xanthene dye) is preferably a compoundrepresented by General Formula (A5).

In General Formula (A5), R²⁰ to R²³ each independently represent ahydrogen atom, an aliphatic hydrocarbon group, or an aromatichydrocarbon group; and A is an anionic moiety represented by any one ofthe following General Formula (AN-1) to (AN-4);

In General Formula (AN-1), * represents a bonding site to a xanthenestructure; and Rf₁ represents an aliphatic hydrocarbon group, ahalogenated aliphatic hydrocarbon group, an aromatic hydrocarbon group,or a halogenated aromatic hydrocarbon group;

in General Formula (AN-2), * represents a bonding site to a xanthenestructure; and Rf₂ represents a halogenated aliphatic hydrocarbon group;

in General Formula (AN-3). * represents a bonding site to a xanthenestructure; Rf₃ represents an aliphatic hydrocarbon group, a halogenatedaliphatic hydrocarbon group, an aromatic hydrocarbon group, or ahalogenated aromatic hydrocarbon group; and B represents a substituent;

in General Formula (AN-4), * represents a bonding site to a xanthenestructure; Rf₄ represents a halogenated aliphatic hydrocarbon group; andB represents a substituent.

In General Formula (A5), R²⁰ preferably represents a hydrogen atom or analiphatic hydrocarbon group, and more preferably a hydrogen atom. Thenumber of carbon atoms of the aliphatic hydrocarbon group is preferably1 to 6, and more preferably 1 to 3. The aliphatic hydrocarbon group ispreferably an alkyl group. The aliphatic hydrocarbon group may have asubstituent. Examples of the substituent include the substituent group Awhich will be described later.

In General Formula (A5), R²¹ preferably represents an aliphatichydrocarbon group or an aromatic hydrocarbon group, and more preferablyan aromatic hydrocarbon group. The number of carbon atoms of thealiphatic hydrocarbon group is preferably 1 to 6, and more preferably 1to 3. The aliphatic hydrocarbon group is preferably an alkyl group. Thearomatic hydrocarbon group may be monocyclic or polycyclic, andpreferably monocyclic. The number of carbon atoms of the aromatichydrocarbon group carbon atoms is preferably 6 to 15, and morepreferably 6 to 12. The aromatic hydrocarbon group is preferably an arylgroup. The number of carbon atoms of the aromatic hydrocarbon group ispreferably 6 to 12, and more preferably 6 to 9. The aliphatichydrocarbon group and aromatic hydrocarbon group may have a substituent.Examples of the substituent include the substituent group A which willbe described later.

In General Formula (A5), R²² has the same definition as R²⁰ in GeneralFormula (A5), and a preferred range thereof is also the same.

In General Formula (A5), R²³ has the same definition as R²¹ in GeneralFormula (A5), and a preferred range thereof is also the same.

In General Formula (AN-1), in the case where Rf₁ represents an aliphatichydrocarbon group, the number of carbon atoms of the aliphatichydrocarbon group is preferably 1 to 6, more preferably 1 to 3, andstill more preferably 1 or 2. The aliphatic hydrocarbon group ispreferably a methyl group.

In General Formula (AN-1), in the case where Rf₁ represents ahalogenated aliphatic hydrocarbon group, the number of carbon atoms ofthe aliphatic hydrocarbon group is preferably 1 to 6, more preferably 1to 3, and still more preferably 1 or 2. The halogenated aliphatichydrocarbon group is preferably a fluorine atom-substituted alkyl group,and more preferably a perfluoroalkyl group.

In General Formula (AN-1), in the case where Rf₁ represents an aromatichydrocarbon group, it may be monocyclic or polycyclic, and preferablymonocyclic. The number of carbon atoms of the aromatic hydrocarbon groupis preferably 6 to 12, and more preferably 6 to 9. The aromatichydrocarbon group is preferably a phenyl group.

In General Formula (AN-1), in the case where Rf_(t) represents ahalogenated aromatic hydrocarbon group, it may be monocyclic orpolycyclic, and preferably monocyclic. The number of carbon atoms of thearomatic hydrocarbon group is preferably 6 to 12, and more preferably 6to 9. The halogenated aromatic hydrocarbon group is preferably afluorine atom-substituted aryl group, and more preferably aperfluoroaryl group.

In General Formula (AN-2), Rf₂ represents a halogenated aliphatichydrocarbon group, and has the same definition as in the case where Rf₁in General Formula (AN-1) represents a halogenated aliphatic hydrocarbongroup, and a preferred range thereof is also the same.

In General Formula (AN-3), in the case where Rf₃ represents an aliphatichydrocarbon group, the number of carbon atoms of the aliphatichydrocarbon group is preferably 1 to 6, more preferably 1 to 3, andstill more preferably 1 or 2.

In General Formula (AN-3), in the case where Rf₃ represents ahalogenated aliphatic hydrocarbon group, the number of carbon atoms ofthe aliphatic hydrocarbon group is preferably 1 to 6, and morepreferably 1 to 3. The halogenated aliphatic hydrocarbon group ispreferably a fluorine atom-substituted alkylene group, and morepreferably a perfluoroalkylene group.

In General Formula (AN-3), in the case where Rf₃ represents an aromatichydrocarbon group, it may be monocyclic or polycyclic, and preferablymonocyclic. The number of carbon atoms of the aromatic hydrocarbon groupis preferably 6 to 12, and more preferably 6 to 9.

In General Formula (AN-3), in the case where Rf₃ represents ahalogenated aromatic hydrocarbon group, it may be monocyclic orpolycyclic, and preferably monocyclic. The number of carbon atoms of thearomatic hydrocarbon group is preferably 6 to 12, and more preferably 6to 9. The halogenated aromatic hydrocarbon group is preferably afluorine atom-substituted arylene group, and more preferably aperfluoroarylene group.

In General Formula (AN-3), B represents a substituent, and preferablycontains a crosslinkable group. The crosslinkable group is preferably atleast one of a polymerizable group (for example, a (meth)acryloyloxygroup and a vinyl group), a leaving group (for example, a fluorinegroup, a chlorine group, a bromine group, an iodine group, and a tosylgroup), a hydroxyl group, a thiol group, an amino group, and a carboxylgroup. In particular. B in General Formula (AN-3) is preferably a groupformed by combination of a crosslinkable group and a linking group.Specifically, it is preferably a group formed by combination of acrosslinkable group and at least one linking group selected from analkylene group having 1 to 6 carbon atoms, an arylene group having 6 to12 carbon atoms, —O—, —S—, —CO—, —SO—, —SO₂—, and —NR—. R in —NR— ispreferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

In General Formula (AN-4), Rf₄ represents a halogenated aliphatichydrocarbon group, and has the same definition as in the case where Rf₃General Formula (AN-3) represents a halogenated aliphatic hydrocarbongroup, and a preferred range thereof is also the same.

In General Formula (AN-4), B has the same definition as B in GeneralFormula (AN-3), and a preferred range thereof is also the same.

<Polymeric Xanthene Compound>

The polymeric xanthene compound which is used in the present inventionpreferably contains a structural unit represented by the followingGeneral Formula (A). The structural unit represented by General Formula(A) may be one kind or two or more kinds, or a combination thereof. Inaddition, it may also contain another structural unit as describedlater.

(In General Formula (A), X₁ represents a linking group formed bypolymerization, and L₁ represents a single bond or a divalent linkinggroup. DyeI represents a dye structure.)

Hereinafter, General Formula (A) will be described in detail.

In General Formula (A), X₁ represents a linking group formed bypolymerization. That is, X¹ represents a portion that forms a repeatingunit corresponding to a main chain formed by a polymerization reaction.Moreover, the moiety represented by two *s is a repeating unit. X₁ isnot particularly limited as long as it is a linking group formed of aknown polymerizable monomer. In particular, X¹ is preferably a linkinggroup represented by the following (XX-1) to (XX-24), more preferablyselected from (meth)acryl-based linking chains represented by (XX-1) and(XX-2), styrene-based linking chains represented by (XX-10) to (XX-17),and a vinyl-based linking chain represented by (XX-24), and still morepreferably selected from (meth)acryl-based linking chains represented by(XX-1) and (XX-2), or a styrene-based linking chain represented by(XX-11).

In (XX-1) to (XX-24), * represents a moiety through which the linkinggroups are linked to L₁.

Me represents a methyl group. Further, R in (XX-18) and (XX-19)represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms,or a phenyl group.

In General Formula (A), L₁ represents a single bond or a divalentlinking group. The divalent linking group in the case where L₁represents a divalent linking group represents a substituted orunsubstituted alkylene group having 1 to 30 carbon atoms (for example, amethylene group, an ethylene group, a trimethylene group, a propylenegroup, or a butylene group), a substituted or unsubstituted arylenegroup having 6 to 30 carbon atoms (for example, a phenylene group or anaphthalene group), a substituted or unsubstituted heterocyclic linkinggroup, —CH═CH—, —O—, —S—, —C(═O)—, —CO₂—, —NR—, —CONR—, —O₂C—, —SO—,—SO₂—, and a linking group formed of two or more of these linked to eachother. Here, R's each independently represent a hydrogen atom, an alkylgroup, an aryl group, or a heterocyclic group.

In General Formula (A), DyeI represents a dye structure derived from theaforementioned dye compound.

The dye multimer having the structural unit represented by GeneralFormula (A) can be synthesized by (1) a method of synthesizing themultimer by means of addition polymerization using a monomer having adye residue, or (2) a method of synthesizing the multimer by causing areaction between a polymer, which has a highly reactive functional groupsuch as an isocyanate group, an acid anhydride group, or an epoxy group,and a dye which has a functional group (a hydroxyl group, a primary orsecondary amino group, a carboxyl group, or the like) that can reactwith the highly reactive group.

The addition polymerization can be performed by applying known additionpolymerization techniques (radical polymerization, anionicpolymerization, and cationic polymerization), among which radicalpolymerization is especially preferred because of milder reactionconditions enough to protect the dye structure against degradation. Forradical polymerization, known reaction conditions can be applied.

Among these, the dye multimer having a structural unit represented byGeneral Formula (A) in the present invention is preferably a radicalpolymer obtained by radically polymerizing a dye monomer containing anethylenically unsaturated bond from the viewpoint of heat resistance.

The polymeric xanthene compound is preferably a polymer having arepeating unit represented by General Formula (A4-1) and/or GeneralFormula (A4-3), and more preferably a polymer having the repeating unitrepresented by General Formula (A4-3).

(In General Formula (A4-1), one of R¹⁰ to R¹⁴ represents a repeatingunit represented by the following General Formula (A4-1-2), at least oneof R¹⁰ to R¹⁴ is a group represented by the following General Formula(A4-1-1), and the remainders of R¹⁰ to R¹⁴ each independently representa hydrogen atom, an aliphatic hydrocarbon group, or an aromatichydrocarbon group.)

(In General Formula (A4-1-1), L¹ represents a single bond or a divalentlinking group. L² represents —SO₂— or —CO—. G represents a carbon atomor a nitrogen atom. n1 represents 2 in the case where G is a carbon atomand represents 1 in the case where G is a nitrogen atom. R⁶ representsan alkyl group containing a fluorine atom or an aryl group containing afluorine atom. In the case where n1 is 2, two R⁶'s may be the same as ordifferent from each other.)

(In General Formula (A4-1-2), L¹¹ represents a single bond or a divalentlinking group. R^(X) represents a hydrogen atom, a methyl group, ahydroxymethyl group, or an alkoxymethyl group.)

(In General Formula (A4-3), four of R¹⁰ to R¹⁴ each independentlyrepresent a hydrogen atom, an aliphatic hydrocarbon group, or anaromatic hydrocarbon group, and one of R¹⁰ to R¹⁴ is a repeating unitrepresented by the following General Formula (A4-3-1).)

(In General Formula (A4-3-1), L¹ represents a single bond or a divalentlinking group. L² represents —SO₂— or —CO—; L³ represents a divalentlinking group. G represents a carbon atom or a nitrogen atom; in thecase where G is a carbon atom, n2 represents 1, and in the case where Grepresents a nitrogen atom. n2 represents 0. R^(7A) and R^(7B) eachindependently represent an alkylene group containing a fluorine atom oran arylene group containing a fluorine atom. R^(X) represents a hydrogenatom, a methyl group, a hydroxymethyl group, or an alkoxymethyl group.)

In General Formula (A4-1), in the case where R¹⁰ to R¹⁴ represent analiphatic hydrocarbon group, the group is preferably an alkyl group. Thenumber of carbon atoms of the aliphatic hydrocarbon group is preferably1 to 6, and more preferably 1 to 3, and the group is still morepreferably a methyl group or an ethyl group.

In General Formula (A4-1), in the case where R¹⁰ to R¹⁴ represent anaromatic hydrocarbon group, the group is preferably an aryl group. Thearomatic hydrocarbon group may be monocyclic or polycyclic, andpreferably monocyclic. The number of carbon atoms of the aromatichydrocarbon group is preferably 6 to 12, and more preferably 6 to 9.

The aliphatic hydrocarbon group and the aromatic hydrocarbon group mayhave a substituent. Examples of the substituent include the substituentgroup A which will be described later.

In General Formula (A4-1-1), L¹ represents a single bond or a divalentlinking group, and it is preferably a single bond. Examples of thedivalent linking group include an alkylene group having 1 to 6 carbonatoms, an arylene group having 6 to 12 carbon atoms, —O—, —S—, or agroup formed by combination of these groups.

In General Formula (A4-1-1), R⁶ represents an alkyl group containing afluorine atom or an aryl group containing a fluorine atom, and has thesame definition as in the case where R⁶ in General Formula (A3-1)represents an alkyl group containing a fluorine atom or an aryl groupcontaining a fluorine atom, and a preferred range thereof is also thesame.

In General Formula (A4-1-2), L¹¹ represents a single bond or a divalentlinking group. Examples of the divalent linking group include analkylene group having 1 to 6 carbon atoms, an arylene group having 6 to18 carbon atoms, —O—, —CO—, —S—, —SO₂—, —NR^(A)R^(B)—, and a groupformed by combination of these groups. The alkylene group having 1 to 6carbon atoms may be linear, branched, or cyclic. The arylene grouphaving 6 to 18 carbon atoms may be monocyclic or polycyclic. In—NR^(A)R^(B)—, R^(A) and R^(B) each independently represent a hydrogenatom or an alkyl group having 1 to 6 carbon atoms, and R^(A) and R^(B)may be bonded to each other to form a ring.

In General Formula (A4-1-2), R^(X) represents a hydrogen atom, a methylgroup, a hydroxymethyl group, or an alkoxymethyl group, and it ispreferably a hydrogen atom or a methyl group. In the case where R^(X)represents an alkoxymethyl group, the number of carbon atoms of thealkoxymethyl group is preferably 1 to 3.

In General Formula (A4-3), four of R¹⁰ to R¹⁴ each independentlyrepresent a hydrogen atom, an aliphatic hydrocarbon group, or anaromatic hydrocarbon group, and one of R¹⁰ to R¹⁴ is a repeating unitrepresented by General Formula (A4-3-1). In particular, R¹⁴ ispreferably a group represented by General Formula (A4-3-1). Thealiphatic hydrocarbon group and aromatic hydrocarbon group has the samedefinition as R¹⁰ to R¹⁴ in General Formula (A4-1), and a preferredrange thereof is also the same.

In General Formula (A4-3-1), L¹ represents a single bond or a divalentlinking group, and it is preferably a single bond. The divalent linkinggroup has the same definition as L¹ in General Formula (A4-1-1).

In General Formula (A4-3-1), L³ represents a divalent linking group. Thedivalent linking group has the same definition as in the case where L¹¹in General Formula (A4-1-2) represents a divalent linking group, and itis preferably an arylene group having 6 to 18 carbon atoms (preferably aphenylene group), —O—, —CO—, —S—, —NR^(A)R^(B)—, or a group formed bycombination of these groups, and more preferably a group formed bycombination of a phenylene group, —O—, and —CO—. —NR^(A)R^(B)— has thesame definition as —NR^(A)R^(B)— described in L¹¹ in General Formula(A4-1-2).

In General Formula (A4-3-1). R^(7A) and R^(7B) each independentlyrepresent an alkylene group containing a fluorine atom or an arylenegroup containing a fluorine atom and have the same definition as in thecase where R⁷ in General Formula (A3-2) represents an alkylene groupcontaining a fluorine atom or arylene containing a fluorine atom, and apreferred range thereof is also the same.

In General Formula (A4-3-1), R^(X) represents a hydrogen atom, a methylgroup, a hydroxymethyl group, or an alkoxymethyl group and has the samedefinition as R^(X) in General Formula (A4-1-2), and a preferred rangethereof is also the same.

Moreover, the polymeric xanthene compound may be a polymer having atleast any one of repeating units represented by General Formula (A4-1),General Formula (A4-3), and the following General Formula (A4-1a).

In General Formula (A4-1a), one of R¹⁰ to R¹⁴ is a repeating unitrepresented by General Formula (A4-1-2), at least one of R¹⁰ to R¹⁴ is agroup represented by General Formula (A4-1-1), and the remainders of R¹⁰to R¹³ each independently represent a hydrogen atom, an aliphatichydrocarbon group, or an aromatic hydrocarbon group. Further, theremainders of R¹⁴, and R¹⁵ to R²⁰ each independently represent ahydrogen atom, halogen atom, an aliphatic hydrocarbon group, or anaromatic hydrocarbon group. n represents an integer of 0 to 5. R¹⁰ andR¹⁵, R¹¹ and R¹⁶, R¹² and R¹⁸, R¹³ and R¹⁹, and a plurality of R¹⁴'s maybe bonded to each other to form a ring.

In General Formula (A4-1a), in the case where R¹⁰ to R²⁰ represent analiphatic hydrocarbon group or an aromatic hydrocarbon group and has thesame definition as in the case where R¹⁰ to R¹⁴ in General Formula(A4-1) represent an aliphatic hydrocarbon group or an aromatichydrocarbon group, and a preferred range thereof is also the same.

The polymeric xanthene compound may have other repeating units, inaddition to the repeating unit represented by General Formula (A4-3).Examples of the other repeating units include a repeating unitcontaining at least one of a polymerizable group, an acid group, and analkali-soluble group.

The polymeric xanthene compound which is used in the present inventionpreferably contains a repeating unit having a polymerizable group. Inthe case where the polymeric xanthene compound which is used in thepresent invention contains a repeating unit having a polymerizablegroup, the amount thereof is, for example, preferably 1 mole to 60moles, and more preferably 10 moles to 50 moles, with respect to 100moles of the entire repeating units.

The acid value of the repeating unit having an acid group is preferably5 mgKOH/g to 200 mgKOH/g, more preferably 10 mgKOH/g to 180 mgKOH/g, andstill more preferably 20 mgKOH/g to 170 mgKOH/g. The acid value can becalculated by, for example, the average content of acid groups in thepolymeric xanthene compound.

In the case where the polymeric xanthene compound contains a repeatingunit having a polymerizable group. The amount thereof is, for example,preferably 1 mole to 90 moles, and more preferably 5 moles to 80 moles,with respect to 100 moles of the entire repeating units.

In the case where the polymeric xanthene compound contains a repeatingunit having an acid group as the repeating unit represented by GeneralFormula (A4-3), the proportion of the repeating unit having an acidgroup is, for example, preferably 5 moles to 90 moles, and morepreferably 10 moles to 80 moles, with respect to 100 moles of therepeating units represented by General Formula (A4-3).

Specific examples of the repeating unit which may be contained in thepolymeric xanthene compound are shown below, but the present inventionis not limited thereto.

The weight-average molecular weight of the polymeric xanthene compoundis preferably 2,000 to 40,000, more preferably 3,000 to 35,000, andparticularly preferably 4.000 to 30,000.

In the present specification, the weight average molecular weight andthe number-average molecular weight are defined as a value in terms ofpolystyrene by GPC measurement. In the present specification, theweight-average molecular weight (Mw) and the number-average molecularweight (Mn) can be determined with, for example, HLC-8220 GPC(manufactured by Tosoh Corporation) by using TSKgel Super AWM-H(manufactured by Tosoh Corporation, 6.0 mm ID×15.0 cm) as a column and a10 mmol/L solution of lithium bromide in N-methylpyrrolidone (NMP) as aneluent.

Further, the ratio [(Mw)/(Mn)] of the weight average molecular weight(Mw) to the number-average molecular weight (Mn) is preferably 1.0 to3.0, more preferably 1.6 to 2.5, and particularly preferably 1.6 to 2.0.

The glass transition temperature (Tg) of the polymeric xanthene compoundwhich is used in the present invention is preferably 50° C. or higher,and more preferably 100° C. or higher. Further, a 5% weight reductiontemperature measured by thermogravimetric analysis (TGA measurement) ispreferably 120° C. or higher, more preferably 150° C. or higher, andstill more preferably 200° C. or higher.

In addition, the absorption coefficient (hereinafter described as ε′.ε′=ε/average molecular weight, unit: L/g·cm) per unit weight of the dyecompound (A) according to the present invention is preferably 30 ormore, more preferably 60 or more, and still more preferably 100 or more.If the absorption coefficient is within the above range, in the casewhere a color filter is manufactured using the colored composition ofthe present invention, a color filter having excellent colorreproducibility can be manufactured.

The maximum absorption wavelength of the dye compound (A) which is usedin the present invention is preferably 400 nm to 650 nm, and morepreferably 450 nm to 600 nm.

In the colored composition of the present invention, the dye compound(A) which is used in the present invention may be used alone or incombination of two or more kinds thereof. In the case of using two ormore kinds of the dye compound (A), the total amount thereof preferablycorresponds to the content which will be described later.

The blending amount of the dye compound (A) in the colored compositionof the present invention is preferably 5% by mass to 60% by mass, andmore preferably 10% by mass to 40% by mass, of the total solid contentof the composition.

Furthermore, the content of the dye compound (A) in the coloredcomposition of the present invention is preferably set in considerationof the content ratio of the dye compound (A) to the pigment. The massratio of the dye compound (A) to the pigment is preferably 10% to 50%,more preferably 15% to 45%, and still more preferably 20% to 40%.

For the dye compound (A) which is used in the present invention, ahydrogen atom in the dye structure may be substituted with a substituentselected from the following substituent group A as long as there is nodeviation from the gist of the present invention.

Substituent Group A:

Examples of the substituent which may be contained in the dye include ahalogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, acycloalkenyl group, an alkynyl group, an aryl group, a heterocyclicgroup, a cyano group, a hydroxyl group, a nitro group, a carboxyl group,an alkoxy group, an aryloxy group, a silyloxy group, a heterocyclic oxygroup, an acyloxy group, a carbamoyloxy group, an amino group (includingan alkylamino group and an anilino group), an acylamino group, anaminocarbonylamino group, an alkoxycarbonylamino group, anaryloxycarbonylamino group, a sulfamoylamino group, analkylsulfonylamino or arylsulfonylamino group, a mercapto group, analkylthio group, an arylthio group, a heterocyclic thio group, asulfamoyl group, a sulfo group, an alkylsulfinyl or arylsulfinyl group,an alkylsulfonyl or arylsulfonyl group, an acyl group, anaryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, anarylazo or heterocyclic azo group, an imide group, a phosphino group, aphosphinyl group, a phosphinyloxy group, a phosphinylamino group, and asilyl group. These will be described in detail below.

Examples of the substituent include a halogen atom (for example, afluorine atom, a chlorine atom, a bromine atom, and an iodine atom), alinear or branched alkyl group (a linear or branched substituted orunsubstituted alkyl group, and preferably an alkyl group having 1 to 30carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl,tert-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, and 2-ethylhexyl), acycloalkyl group (preferably a substituted or unsubstituted cycloalkylgroup having 3 to 30 carbon atoms, for example, cyclohexyl andcyclopentyl, or a polycycloalkyl group, for example, a group having apolycyclic structure such as a bicycloalkyl group (preferably asubstituted or unsubstituted bicycloalkyl group having 5 to 30 carbonatoms, for example, bicyclo[1,2,2]heptan-2-yl andbicyclo[2,2,2]octan-3-yl), and a tricycloalkyl group. Among these, amonocyclic cycloalkyl group and a bicycloalkyl group are morepreferable, and a monocyclic cycloalkyl group is particularlypreferable),

a linear or branched alkenyl group (a linear or branched substituted orunsubstituted alkenyl group, which is preferably an alkenyl group having2 to 30 carbon atoms, for example, vinyl, allyl, prenyl, geranyl, andoleyl), a cycloalkenyl group (preferably a substituted or unsubstitutedcycloalkenyl group having 3 to 30 carbon atoms, for example,2-cyclopenten-1-yl and 2-cyclohexen-1-yl, a polycyclic alkenyl group forexample, a bicycloalkenyl group (preferably a substituted orunsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, forexample, bicyclo[2,2,1]hepto-2-en-1-yl andbicyclo[2,2,2]octo-2-en-4-yl), or a tricycloalkenyl group. Among these,a monocyclic cycloalkenyl group is particularly preferable) an alkynylgroup (preferably a substituted or unsubstituted alkynyl group having 2to 30 carbon atoms, for example, an ethynyl group, a propargyl group,and a trimethylsilylethynyl group),

an aryl group (preferably a substituted or unsubstituted aryl grouphaving 6 to 30 carbon atoms, for example, phenyl, p-tolyl, naphthyl,m-chlorophenyl, and o-hexadecanoylaminophenyl), a heterocyclic group(preferably a substituted or unsubstituted, saturated or unsaturated,aromatic or non-aromatic, and monocyclic or ring-fused 5- to 7-memberedheterocyclic group, more preferably a heterocyclic group of whichring-constituting atoms are selected from a carbon atom, a nitrogenatom, and a sulfur atom, and which has at least any one of hetero atomsincluding a nitrogen atom, an oxygen atom, and a sulfur atom, and stillmore preferably a 5- or 6-membered aromatic heterocyclic group having 3to 30 carbon atoms, for example, 2-furyl, 2-thienyl, 2-pyridyl,4-pyridyl, 2-pyrimidinyl, and 2-benzothiazolyl), a cyano group, ahydroxyl group, a nitro group, a carboxyl group,

an alkoxy group (preferably a substituted or unsubstituted alkoxy grouphaving 1 to 30 carbon atoms, for example, methoxy, ethoxy, isopropoxy,tert-butoxy, n-octyloxy, and 2-methoxyethoxy), an aryloxy group(preferably a substituted or unsubstituted aryloxy group having 6 to 30carbon atoms, for example, phenoxy, 2-methylphenoxy,2,4-di-tert-amylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, and2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxygroup having 3 to 20 carbon atoms, for example, trimethylsilyloxy andtert-butyldimethylsilyloxy), a heterocyclic oxy group (preferably asubstituted or unsubstituted heterocyclic oxy group having 2 to 30carbon atoms, with heterocyclic moiety being preferably the heterocyclicmoiety explained for the aforementioned heterocyclic group and theheterocyclic oxy group being, for example, 1-phenyltetrazol-5-oxy or2-tetrahydropyranyloxy),

an acyloxy group (preferably a formyloxy group, a substituted orunsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, and asubstituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbonatoms, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy,benzoyloxy, and p-methoxyphenylcarbonyloxy), a carbamoyloxy group(preferably a substituted or unsubstituted carbamoyloxy group having 1to 30 carbon atoms, for example, N,N-dimethylcarbamoyloxy,N,N-diethylcarbamoyloxy, morpholinocarbonyloxy,N,N-di-n-octylaminocarbonyloxy, and N-n-octylcarbamoyloxy), analkoxycarbonyloxy group (preferably a substituted or unsubstitutedalkoxycarbonyloxy group having 2 to 30 carbon atoms, for example,methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, andn-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably asubstituted or unsubstituted aryloxycarbonyloxy group having 7 to 30carbon atoms, for example, phenoxycarbonyloxy,p-methoxyphenoxycarbonyloxy, and p-n-hexadecyloxyphenoxycarbonyloxy),

an amino group (preferably an amino group, a substituted orunsubstituted alkylamino group having 1 to 30 carbon atoms, asubstituted or unsubstituted arylamino group having 6 to 30 carbonatoms, and a heterocyclic amino group having 0 to 30 carbon atoms, forexample, amino, methylamino, dimethylamino, anilino, N-methyl-anilino,diphenylamino, and N-1,3,5-triazin-2-ylamino), an acylamino group(preferably a formylamino group, a substituted or unsubstitutedalkylcarbonylamino group having 1 to 30 carbon atoms, and a substitutedor unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms,for example, formylamino, acetylamino, pivaloylamino, lauroylamino,benzoylamino, and 3,4,5-tri-n-octyloxyphenylcarbonylamino), anaminocarbonylamino group (preferably a substituted or unsubstitutedaminocarbonylamino group having 1 to 30 carbon atoms, for example,carbamoylamino, N,N-dimethylaminocarbonylamino,N,N-diethylaminocarbonylamino, and morpholinocarbonylamino), analkoxycarbonylamino group (preferably a substituted or unsubstitutedalkoxycarbonylamino group having 2 to 30 carbon atoms, for example,methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino,n-octadecyloxycarbonylamino, and N-methyl-methoxycarbonylamino),

an aryloxycarbonylamino group (preferably a substituted or unsubstitutedaryloxycarbonylamino group having 7 to 30 carbon atoms, for example,phenoxycarbonylamino, p-chlorophenoxycarbonylamino, andm-n-octyloxyphenoxycarbonylamino), a sulfamoylamino group (preferably asubstituted or unsubstituted sulfamoylamino group having 0 to 30 carbonatoms, for example, sulfamoylamino, N,N-dimethylaminosulfonylamino, andN-n-octylaminosulfonylamino), an alkylsulfonylamino or arylsulfonylaminogroup (preferably a substituted or unsubstituted alkylsulfonylaminogroup having 1 to 30 carbon atoms, or a substituted or unsubstitutedarylsulfonylamino group having 6 to 30 carbon atoms, for example,methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino,2,3,5-trichlorophenylsulfonylamino, and p-methylphenylsulfonylamino), amercapto group,

an alkylthio group (preferably a substituted or unsubstituted alkylthiogroup having 1 to 30 carbon atoms, for example, methylthio, ethylthio,and n-hexadecylthio), an arylthio group (preferably a substituted orunsubstituted arylthio group having 6 to 30 carbon atoms, for example,phenylthio, p-chlorophenylthio, and m-methoxyphenylthio), a heterocyclicthio group (preferably a substituted or unsubstituted heterocyclic thiogroup having 2 to 30 carbon atoms, in which a heterocyclic moiety ispreferably the heterocyclic moiety explained for the aforementionedheterocyclic group, for example, 2-benzothiazolylthio and1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substitutedor unsubstituted sulfamoyl group having 0 to 30 carbon atoms, forexample, N-ethylsulfamoyl, N-(3-dodecyloxypropyl)sulfamoyl,N,N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, andN—(N′-phenylcarbamoyl)sulfamoyl), a sulfo group,

an alkylsulfinyl or arylsulfinyl group (preferably a substituted orunsubstituted alkylsulfinyl group having 1 to 30 carbon atoms or asubstituted or unsubstituted arylsulfinyl group having 6 to 30 carbonatoms, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, andp-methylphenylsulfinyl), an alkylsulfonyl or arylsulfonyl group(preferably a substituted or unsubstituted alkylsulfonyl group having 1to 30 carbon atoms or a substituted or unsubstituted arylsulfonyl grouphaving 6 to 30 carbon atoms, for example, methylsulfonyl, ethylsulfonyl,phenylsulfonyl, and p-methylphenylsulfonyl), an acyl group (preferably aformyl group, a substituted or unsubstituted alkylcarbonyl group having2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonylgroup having 7 to 30 carbon atoms, for example, acetyl, pivaloyl,2-chloroacetyl, stearoyl, benzoyl, and p-n-octyloxyphenylcarbonyl), anaryloxycarbonyl group (preferably a substituted or unsubstitutedaryloxycarbonyl group having 7 to 30 carbon atoms, for example,phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, andp-tert-butylphenoxycarbonyl),

an alkoxycarbonyl group (preferably a substituted or unsubstitutedalkoxycarbonyl group having 2 to 30 carbon atoms, for example,methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, andn-octadecyloxycarbonyl), a carbamoyl group (preferably substituted orunsubstituted carbamoyl having 1 to 30 carbon atoms, for example,carbamoyl, N-methylcarbamoyl, N,N-dimethylcarbamoyl,N,N-di-n-octylcarbamoyl, and N-(methylsulfonyl)carbamoyl), an arylazo orheterocyclic azo group (preferably a substituted or unsubstitutedarylazo group having 6 to 30 carbon atoms, or a substituted orunsubstituted heterocyclic azo group having 3 to 30 carbon atoms (inwhich a heterocyclic moiety is preferably the heterocyclic moietyexplained for the aforementioned heterocyclic group), for example,phenylazo, p-chlorophenylazo, and 5-ethylthio-1,3,4-thiadiazol-2-ylazo),an imide group (preferably a substituted or unsubstituted imide grouphaving 2 to 30 carbon atoms, for example, N-succinimide andN-phthalimide), a phosphino group (preferably a substituted orunsubstituted phosphino group having 2 to 30 carbon atoms, for example,dimethylphosphino, diphenylphosphino, and methylphenoxyphosphino), aphosphinyl group (preferably a substituted or unsubstituted phosphinylgroup having 2 to 30 carbon atoms, for example, phosphinyl,dioctyloxyphosphinyl, and diethoxyphosphinyl),

a phosphinyloxy group (preferably a substituted or unsubstitutedphosphinyloxy group having 2 to 30 carbon atoms, for example,diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy), a phosphinylaminogroup (preferably a substituted or unsubstituted phosphinylamino grouphaving 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino anddimethylaminophosphinylamino), and a silyl group (preferably asubstituted or unsubstituted silyl group having 3 to 30 carbon atoms,for example, trimethylsilyl, tert-butyldimethylsilyl, andphenyldimethylsilyl).

Among the above functional groups, in the functional groups havinghydrogen atoms, the portion of hydrogen atoms in the functional groupsmay be substituted with any one of the above groups. Examples of thefunctional groups which can be introduced as substituents include analkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, analkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonylgroup, and specific examples thereof include amethylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonylgroup, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.

Specific examples of the dye compound (A) which is used in the presentinvention are shown below, but the present invention is not limitedthereto. Further, among the following compounds, polymers containingrepeating units derived from compounds (A-13 to A-26) containing apolymerizable group are also included in the dye compound (A) of thepresent invention.

<<Cyanine Dye>>

One of the embodiments of the dye compound (A) is one having a partialstructure derived from a cyanine dye (cyanine compound). Examples of thedye compound (A) include a dye compound which has a partial structurederived from a compound represented by the following General Formula(PM) (cyanine compound) as the partial structure of the dye site. Thecyanine compounds in the present invention collectively refer tocompounds having a dye site containing a cyanine skeleton in themolecule.

(In General Formula (PM), a ring Z1 and a ring Z2 each independentlyrepresent a heterocycle which may have a substituent. 1 represents aninteger of 0 to 3.)

Examples of the ring Z1 and the ring Z2 each independently includeoxazole, benzoxazole, oxazoline, thiazole, thiazoline, benzothiazole,indolenine, benzoindolenine, and 1,3-thiadiazine.

Examples of the substituents which may be contained in the ring Z1 andthe ring Z2 include the substituent group A which will be describedlater.

The compound represented by General Formula (PM) is preferably acompound represented by the following General Formula (PM-2).

(In General Formula (PM-2), the ring Z⁵ and the ring Z⁶ eachindependently represent a benzene ring which may have a substituent or anaphthalene ring which may have a substituent.

n represents an integer of 0 to 3.

A¹ and A² each independently represent an oxygen atom, a sulfur atom, aselenium atom, a carbon atom, or a nitrogen atom.

R¹ and R² each independently represent a monovalent aliphatichydrocarbon group having 1 to 20 carbon atoms, which may have asubstituent.

R³ and R⁴ each independently represent a hydrogen atom, a monovalentaliphatic hydrocarbon group having 1 to 6 carbon atoms, or a divalentaliphatic hydrocarbon group having 2 to 6 carbon atoms, which is formedwhen one R³ and one R⁴ are combined with each other.

a and b each independently represent an integer of 0 to 2.)

The following (pm-1) to (pm-17) are examples of the dye structure of thecyanine compound, but the present invention is not limited thereto.

Furthermore, the following A-pm-1 to A-pm-4 are specific examples of thecyanine compound, but the present invention is not limited thereto.Further, polymers containing repeating units derived from compounds(A-pm-1, A-pm-2 and A-pm-4) containing a polymerizable group are alsoincluded in the dye compound (A) of the present invention.

<<Squarylium Dye>>

The dye compound (A) may have a squarylium dye structure. As thesquarylium dye, a dye represented by the following General Formula (K)is preferable.

(In the formula, A and D each independently represent an aryl group or aheterocyclic group, R represents an alkyl group or an aryl group, and Xrepresents a weakly nucleophilic anion structure.)

In General Formula (K), A and D each independently represent an arylgroup or a heterocyclic group, and D is in a cationic structure. Thearyl group is preferably an aryl group having 6 to 48 carbon atoms, andmore preferably an aryl group having 6 to 24 carbon atoms, and examplesthereof include phenyl and naphthyl. The heterocyclic group ispreferably a heterocyclic group of a 5- or 6-membered ring, and examplesthereof include pyrrolyl, imidazoyl, pyrazoyl, thienyl, pyridyl,pyrimidyl, pyridazyl, triazol-1-yl, thienyl, furyl, and thiadiazolyl. Aand B may be a condensed ring of an aryl group and a heterocyclic group.

R represents an alkyl group or an aryl group. The alkyl group ispreferably a linear, branched, or cyclic alkyl group preferably having 1to 36 carbon atoms, and more preferably having 1 to 12 carbon atoms, forexample, a methyl group, an ethyl group, a propyl group, an isopropylgroup, a butyl group, an isobutyl group, a tert-butyl group, a hexylgroup, a 2-ethylhexyl group, a dodecyl group, a cyclopropyl group, acyclopentyl group, a cyclohexyl group, and a 1-adamantyl group).Examples of the aryl group include an aryl group preferably having 6 to36 carbon atoms, and more preferably having 6 to 18 carbon atoms, forexample, a phenyl group and a naphthyl group.

As the compound represented by General Formula (K), in particular, acompound represented by the following General Formula (K-1) or thefollowing General Formula (K-2) is preferable.

(In General Formula (K-1), M¹, M², M³, and M⁴ each independentlyrepresent an oxygen atom, a sulfur atom, or a nitrogen atom, and R, R¹,and R² each independently represent an alkyl group or an aryl group.)

In General Formula (K-1), M¹, M², M³, and M⁴ each independentlyrepresent an oxygen atom, a sulfur atom, or a nitrogen atom, among whicha sulfur atom and a nitrogen atom are preferable. M¹ and M³ arepreferably the same atoms, and M² and M⁴ are preferably the same atoms.

R, R¹, and R² in General Formula (K-1) have the same definitions as R inGeneral Formula (K), and preferred ranges thereof are also the same.

(In General Formula (K-2), M⁵ and M⁶ each independently represent anoxygen atom, a sulfur atom, or a nitrogen atom, and R, R¹, R², R³, R⁴,R⁵, and R⁶ each independently represent an alkyl group or an arylgroup.)

In General Formula (K-2), M⁵ and M⁶ have the same definitions as M¹ toM⁴ in General Formula (K-1), and preferred ranges thereof are also thesame. M⁵ and M⁶ are preferably the same atoms.

R, R¹, R², R³, R⁴, R⁵, and R⁶ in General Formula (K-2) have the samedefinitions as R in General Formula (K), and preferred ranges thereofare also the same.

As the compound represented by General Formula (K-1), a compoundrepresented by the following General Formula (K-3) is preferable, and asthe compound represented by General Formula (K-2), a compoundrepresented by the following General Formula (K-4) is preferable.

(In General Formula (K-3), R, R¹, and R² each independently represent analkyl group or an aryl group.)

R, R¹, and R² in General Formula (K-3) have the same definitions as R inGeneral Formula (K), and preferred ranges thereof are also the same.

(In General Formula (K-4), R, R¹, R², R³, R⁴, R⁵, and R⁶ eachindependently represent an alkyl group or an aryl group.)

R, R¹, R², R³, R⁴, R⁵, and R⁶ in General Formula (K-4) have the samedefinitions as R in General Formula (K), and preferred ranges thereofare also the same.

The following (sm-1) and (sm-2) are the examples of the dye structure,but the present invention is not limited thereto.

In addition, the following (sm-3) and (sm-4) are the examples of thesquarylium compound, but the present invention is not limited thereto.

<<<Dipyrromethene Dye>>>

One of the embodiments of the dye compound (A) is a dye compound havinga partial structure derived from a dipyrromethene dye shown below as thepartial structure of a dye site.

As the dipyrromethene dye in the present invention, a dipyrromethenecompound and a dipyrromethene metal complex compound obtained from adipyrromethene compound with a metal or a metal compound are preferable.

Furthermore, in the present invention, a compound having adipyrromethene structure is referred to as a dipyrromethene compound,and a complex in which a metal or a metal compound is coordinated to thecompound having a dipyrromethene structure is referred to as adipyrromethene metal complex compound.

As the dipyrromethene metal complex compound, a dipyrromethene metalcomplex compound obtained from a dipyrromethene compound represented bythe following General Formula (M) with a metal or a metal compound and atautomer thereof are preferable. Among these, a dipyrromethene metalcomplex compound represented by the following General Formula (7) and adipyrromethene metal complex compound represented by the followingGeneral Formula (8) are exemplified as preferred embodiments, and thedipyrromethene metal complex compound represented by the followingGeneral Formula (8) is more preferable.

<<<Dipyrromethene Metal Complex Compound Obtained from DipyrrometheneCompound Represented by General Formula (M) with Metal or a MetalCompound, and Tautomer Thereof>>>

One of the preferred embodiments of the dye structure in the dyecompound (A) is a dye structure which contains, as a dye site, a complex(hereinafter appropriately referred to as a “specific complex”) in whicha compound (dipyrromethene compound) represented by the followingGeneral Formula (M) or a tautomer thereof is coordinated to a metal or ametal compound. In the present invention, the following compound forms acationic structure, and for example, a metal such as zinc, bonded to anitrogen atom of General Formula (M), can form cation.

(In General Formula (M), R⁴ to R¹⁰ each independently represent ahydrogen atom or a monovalent substituent, provided that there is nocase where R⁴ and R⁹ are bonded to each other to form a ring.)

In the case where the compound represented by General Formula (M) isintroduced into structural units represented by General Formulae (A) to(C), or a multimer represented by General Formula (D), which will bedescribed later, the introduction site is not particularly limited.However, in view of synthesis suitability, the compound is preferablyintroduced at any one site of R⁴ to R⁹, more preferably introduced atany one site of R⁴, R⁶. R⁷, and R⁹, and still more preferably introducedat any one site of R⁴ and R⁹.

In the case where R⁴ to R⁹ in General Formula (M) represent a monovalentsubstituent, examples of the monovalent substituent include thesubstituents exemplified in the section of the substituent group A asdescribed above.

In the case where the monovalent substituents represented by R⁴ to R⁹ inGeneral Formula (M) are each a group which can be further substituted,the group may further have the substituent(s) described for R⁴ to R⁹,and in the case where the group has two or more substituents, thesesubstituents may be the same as or different from each other.

In General Formula (M), R⁴ and R⁵, R⁵ and R⁶, R⁷ and R⁸, and R⁸ and R⁹may be each independently bonded to each other to form a 5-, 6-, or7-membered saturated or unsaturated ring. There is no case where R⁴ andR⁹ are bonded to each other to form a ring. In the case where the formed5-, 6-, or 7-membered ring is a group which can be further substituted,the ring may be substituted with the substituents described for R⁴ toR⁹, and in the case where the ring is substituted with two or moresubstituents, these substituents may be the same as or different fromeach other.

In General Formula (M), in the case where R⁴ and R⁵, R⁵ and R⁶, R⁷ andR⁸, and R⁸ and R⁹ are each independently bonded to each other to form a5-, 6-, or 7-membered saturated or unsaturated ring not having asubstituent, examples of the 5-, 6-, or 7-membered saturated orunsaturated ring not having a substituent include a pyrrole ring, afuran ring, a thiophene ring, a pyrazole ring, an imidazole ring, atriazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, apiperidine ring, a cyclopentene ring, a cyclohexene ring, a benzenering, a pyridine ring, a pyrazine ring, and a pyridazine ring, andpreferably a benzene ring or a pyridine ring.

R¹⁰ in General Formula (M) preferably represents a hydrogen atom, ahalogen atom, an alkyl group, an aryl group, or a heterocyclic group.The halogen atom, the alkyl group, the aryl group, and the heterocyclicgroup have the same definitions as those of the halogen atom, the alkylgroup, the aryl group, and the heterocyclic group, respectively,described in the section of the substituent group A as described above,and a preferred range thereof is also the same.

In the case where R¹⁰ represents an alkyl group, an aryl group, or aheterocyclic group, if the alkyl group, the aryl group, and theheterocyclic group are groups which can be further substituted, they maybe substituted with the substituents described in the section of thesubstituent group A as described above. In the case where the groups aresubstituted with two or more substituents, the substituents may be thesame as or different from each other.

˜Metal or Metal Compound˜

The specific complex in the present invention is the complex in whichthe dipyrromethene compound represented by General Formula (M) asdescribed above or a tautomer thereof is coordinated to a metal or ametal compound.

Here, the metal or metal compound may be any types of metal or metalcompound as long as they can form a complex, and examples thereofinclude a divalent metal atom, a divalent metal oxide, a divalent metalhydroxide, and a divalent metal chloride. Examples of the metal or metalcompound include metals such as Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb,Cu, Ni, Co, and Fe, metal chlorides such as AlCl. InCl, FeCl, TiCl₂,SnCl₂, SiCl₂, and GeCl₂, metal oxides such as TiO and VO, and metalhydroxides such as Si(OH)₂.

Among these, in view of the stability, spectral characteristics, heatresistance, light fastness, and production suitability of the complex,Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, or VO is preferable,Zn, Mg. Si. Pt, Pd, Cu, Ni, Co, or VO is more preferable, and Zn isparticularly preferable.

Next, a more preferred range of the specific complex of the compoundrepresented by General Formula (M) in the present invention will bedescribed.

A preferred range of the specific complex in the present invention is arange in which in General Formula (M), R⁴ and R⁹ are each independentlya hydrogen atom, an alkyl group, an alkenyl group, an aryl group, aheterocyclic group, a silyl group, a hydroxyl group, a cyano group, analkoxy group, an aryloxy group, a heterocyclic oxy group, an acyl group,an alkoxycarbonyl group, a carbamoyl group, an amino group, an anilinogroup, a heterocyclic amino group, a carbonamide group, a ureido group,an imide group, an alkoxycarbonylamino group, an aryloxycarbonylaminogroup, a sulfonamide group, an azo group, an alkylthio group, anarylthio group, a heterocyclic thio group, an alkylsulfonyl group, anarylsulfonyl group, or a phosphinoylamino group; R⁵ and R⁸ are eachindependently a hydrogen atom, a halogen atom, an alkyl group, analkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, acyano group, a nitro group, an alkoxy group, an aryloxy group, aheterocyclic oxy group, an acyl group, an alkoxycarbonyl group, anaryloxycarbonyl group, a carbamoyl group, an imide group, analkoxycarbonylamino group, a sulfonamide group, an azo group, analkylthio group, an arylthio group, a heterocyclic thio group, analkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group; R⁶ andR⁷ are each independently a hydrogen atom, a halogen atom, an alkylgroup, an alkenyl group, an aryl group, a heterocyclic group, a silylgroup, a hydroxyl group, a cyano group, an alkoxy group, an aryloxygroup, a heterocyclic oxy group, an acyl group, an alkoxycarbonyl group,a carbamoyl group, an anilino group, a carbonamide group, a ureidogroup, an imide group, an alkoxycarbonylamino group, a sulfonamidegroup, an azo group, an alkylthio group, an arylthio group, aheterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group,a sulfamoyl group, or a phosphinoylamino group; R¹⁰ is a hydrogen atom,a halogen atom, an alkyl group, an aryl group, or a heterocyclic group;and the metal or metal compound is Zn, Mg, Si, Pt, Pd, Mo. Mn, Cu, Ni,Co, TiO, or V═O.

A more preferred range of the specific complex in the present inventionis a range in which in General Formula (M), R⁴ and R⁹ are eachindependently a hydrogen atom, an alkyl group, an alkenyl group, an arylgroup, a heterocyclic group, a cyano group, an acyl group, analkoxycarbonyl group, a carbamoyl group, an amino group, a heterocyclicamino group, a carbonamide group, a ureido group, an imide group, analkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamidegroup, an azo group, an alkylsulfonyl group, an arylsulfonyl group, or aphosphinoylamino group; R⁵ and R⁸ are each independently an alkyl group,an alkenyl group, an aryl group, a heterocyclic group, a cyano group, anitro group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonylgroup, a carbamoyl group, an imide group, an alkylsulfonyl group, anaryl sulfonyl group, or a sulfamoyl group; R⁶ and R⁷ are eachindependently a hydrogen atom, an alkyl group, an alkenyl group, an arylgroup, a heterocyclic group, a cyano group, an acyl group, analkoxycarbonyl group, a carbamoyl group, a carbonamide group, a ureidogroup, an imide group, an alkoxycarbonylamino group, a sulfonamidegroup, an alkylthio group, an arylthio group, a heterocyclic thio group,an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group; R¹⁰is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or aheterocyclic group; and the metal or metal compound is Zn, Mg, Si, Pt,Pd, Cu, Ni, Co, or V═O.

A particularly preferred range of the specific complex in the presentinvention is a range in which in General Formula (M), R⁴ and R⁹ are eacha hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, anamino group, a heterocyclic amino group, a carbonamide group, a ureidogroup, an imide group, an alkoxycarbonylamino group, a sulfonamidegroup, an azo group, an alkylsulfonyl group, an arylsulfonyl group, or aphosphinoylamino group; R⁵ and R⁸ are each independently an alkyl group,an aryl group, a heterocyclic group, a cyano group, an acyl group, analkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, or anarylsulfonyl group; R⁶ and R⁷ are each independently a hydrogen atom, analkyl group, an aryl group, or a heterocyclic group; R¹⁰ is a hydrogenatom, an alkyl group, an aryl group, or a heterocyclic group; and themetal or metal compound is Zn, Cu, Co, or V═O.

Moreover, a dipyrromethene metal complex compound represented by GeneralFormula (7) or (8), which will be described in detail below, is also aparticularly preferred embodiment of the dipyrromethene dye.

<<Dipyrromethene Metal Complex Compound Represented by General Formula(7)>>

One of the suitable embodiments of the dye structure in the dye dimer(A) is a dye structure derived from a dipyrromethene metal complexcompound represented by the following General Formula (7).

(In General Formula (7), R⁴ to R⁹ each independently represent ahydrogen atom or a monovalent substituent, and R¹⁰ represents a hydrogenatom, a halogen atom, an alkyl group, an aryl group, or a heterocyclicgroup. Ma represents a metal atom or a metal compound, provided thatthere is no case where R⁴ and R⁹ are bonded to each other to form aring.)

Incidentally, the dipyrromethene metal complex compound represented byGeneral Formula (7) includes a tautomer.

In the case where the dipyrromethene metal complex compound representedby General Formula (7) is introduced into a multimer, the introductionsite is not particularly limited. However, in view of synthesissuitability, the compound is preferably introduced at any one site of R⁴to R⁹, more preferably introduced at any one site of R⁴, R⁶, R⁷, and R⁹,and still more preferably introduced at any one site of R⁴ and R⁹.

In the case where the dye structure has an alkali-soluble group, as amethod for introducing the alkali-soluble group, a method forintroducing the alkali-soluble group to one, two, or more substituentsout of R⁴ to R¹⁰ in General Formula (7) can be used. Among thesesubstituents, any one of R⁴ to R⁹ and X¹ is preferable, any one of R⁴,R⁶, R⁷, and R⁹ is more preferable, and any one of R⁴ and R⁹ is stillmore preferable.

The dipyrromethene metal complex compound represented by General Formula(7) may have a functional group other than the alkali-soluble group aslong as the effects of the present invention are not diminished.

R⁴ to R⁹ in General Formula (7) have the same definitions as R⁴ to R⁹ inGeneral Formula (M), and preferred embodiments thereof are also thesame.

In General Formula (7), Ma represents a metal atom or a metal compound.The metal atom or metal compound may be any type as long as it is ametal atom or a metal compound which can form a complex, and examplesthereof include a divalent metal atom, a divalent metal oxide, adivalent metal hydroxide, or a divalent metal chloride.

Examples of the metal atom or metal compound include Zn, Mg, Si, Sn, Rh,Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, and Fe; metal chlorides such as AlCl,InCl, FeCl, TiCl₂, SnCl₂, SiCl₂, and GeCl₂; metal oxides such as TiO andV═O; and metal hydroxides such as Si(OH)₂.

Among these, in view of stability, spectral characteristics, heatresistance, light fastness, and production suitability of the complex,as the metal atom or metal compound, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu,Ni, Co, TiO, and V—O are preferable, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, andV═O are more preferable, Zn, Co, V═O, and Cu are still more preferable,and Zn is particularly preferable.

Furthermore, in General Formula (7), R¹⁰ represents a hydrogen atom, ahalogen atom, an alkyl group, an aryl group, or a heterocyclic group,and is preferably a hydrogen atom.

A preferred embodiment of the compound represented by General Formula(7) is an embodiment in which R⁴ to R⁹ are each independently thepreferred embodiments as mentioned in the description of R⁴ to R⁹; andR¹⁰ is the preferred embodiment as mentioned in the description of R¹⁰,and Ma is Zn, Cu, Co, or V═O.

<<<Dipyrromethene Metal Complex Compound Represented by General Formula(8)>>>

One of suitable embodiments of the dye structure in the dye compound (A)is a dye structure derived from a dipyrromethene metal complex compoundrepresented by the following General Formula (8).

(In General Formula (8), R¹¹ and R¹⁶ each independently represent analkyl group, an alkenyl group, an aryl group, a heterocyclic group, analkoxy group, an aryloxy group, an alkylamino group, an arylamino group,or a heterocyclic amino group. R¹² to R¹⁵ each independently represent ahydrogen atom or a substituent. R¹⁷ represents a hydrogen atom, ahalogen atom, an alkyl group, an aryl group, or a heterocyclic group. Marepresents a metal atom or a metal compound. X² and X³ eachindependently represent NR (R represents a hydrogen atom, an alkylgroup, an alkenyl group, an aryl group, a heterocyclic group, an acylgroup, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogenatom, an oxygen atom, or a sulfur atom. Y¹ and Y² each independentlyrepresent NR^(c) (R^(c) represents a hydrogen atom, an alkyl group, analkenyl group, an aryl group, a heterocyclic group, an acyl group, analkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom or acarbon atom. R¹¹ and Y¹ may be bonded to each other to form a 5-, 6-, or7-membered ring, and R¹⁶ and Y² may be bonded to each other to form a5-, 6-, or 7-membered ring.)

Incidentally, the dipyrromethene metal complex compound represented byGeneral Formula (8) includes a tautomer.

The site at which the dipyrromethene metal complex compound representedby General Formula (8) is introduced into a multimer is not particularlylimited as long as the effects of the present invention are notdiminished. However, the site is preferably at least one of R^(1′) toR¹⁷, and Y¹ to Y². Among these, in view of synthesis suitability, it ispreferable that the compound is introduced at one of R¹¹ to R¹⁶. In amore preferred embodiment, the compound is introduced at one of R¹¹,R¹³, R¹⁴, and R¹⁶. In a still more preferred embodiment, the compound isintroduced at one of R¹¹ and R¹⁶.

In the case where the dye structure has an alkali-soluble group, if adye monomer or a structural unit having the alkali-soluble group is usedas a method for introducing the alkali-soluble group, it is possible touse a method for introducing the alkali-soluble group into one, two, ormore substituents out of R¹¹ to R¹⁷, and Y¹ to Y² in General Formula(8). Among these substituents, one of R¹¹ to R¹⁶ is preferable, one ofR¹¹, R¹³, R¹⁴, and R¹⁶ is more preferable, and one of R¹¹ and R¹⁶ isstill more preferable.

The dipyrromethene metal complex compound represented by General Formula(8) may have a functional group other than the alkali-soluble group aslong as the effects of the present invention are not diminished.

In General Formula (8), R¹² to R¹⁵ have the same definitions as R⁵ to R⁸in General Formula (M), and preferred embodiments thereof are also thesame. R¹⁷ has the same definition as R¹⁰ in General Formula (M), andpreferred embodiments thereof are also the same. Ma has the samedefinition as Ma in General Formula (7), and preferred ranges thereofare also the same.

More specifically, among R¹² to R¹⁵ in General Formula (8), as R¹² andR¹⁵, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoylgroup, an alkylsulfonyl group, an arylsulfonyl group, a nitrile group,an imide group, and a carbamoylsulfonyl group are preferable, analkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, analkylsulfonyl group, a nitrile group, an imide group, and acarbamoylsulfonyl group are more preferable, an alkoxycarbonyl group, anaryloxycarbonyl group, a carbamoyl group, a nitrile group, an imidegroup, and a carbamoylsulfonyl group are still more preferable, and analkoxycarbonyl group, an aryloxycarbonyl group, and a carbamoyl groupare particularly preferable.

As R¹³ and R¹⁴, a substituted or unsubstituted alkyl group, asubstituted or unsubstituted aryl group, and a substituted orunsubstituted heterocyclic group are preferable, and a substituted orunsubstituted alkyl group and a substituted or unsubstituted aryl groupare more preferable. Specific examples of the more preferable alkylgroup, an aryl group, and heterocyclic group include the same specificexamples as listed for R⁶ and R⁷ of General Formula (M).

In General Formula (8), R¹¹ and R¹⁶ each represent an alkyl group (alinear, branched, or cyclic alkyl group preferably having 1 to 36 carbonatoms, and more preferably having 1 to 12 carbon atoms, for example, amethyl group, an ethyl group, a propyl group, an isopropyl group, abutyl group, an isobutyl group, a tert-butyl group, a hexyl group, a2-ethylhexyl group, a dodecyl group, a cyclopropyl group, a cyclopentylgroup, a cyclohexyl group, and a 1-adamantyl group), an alkenyl group(an alkenyl group preferably having 2 to 24 carbon atoms, and morepreferably having 2 to 12 carbon atoms, for example, a vinyl group, anallyl group, and a 3-buten-1-yl group), an aryl group (an aryl grouppreferably having 6 to 36 carbon atoms, and more preferably having 6 to18 carbon atoms, for example, a phenyl group and a naphthyl group), aheterocyclic group (a heterocyclic group preferably having 1 to 24carbon atoms, and more preferably having 1 to 12 carbon atoms, forexample, a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, a2-pyrimidinyl group, a 2-pyridyl group, a 2-benzothiazolyl group, a1-imidazolyl group, a 1-pyrazolyl group, and a benzotriazol-1-yl group),an alkoxy group (an alkoxy group preferably having 1 to 36 carbon atoms,and more preferably having 1 to 18 carbon atoms, for example, a methoxygroup, an ethoxy group, a propyloxy group, a butoxy group, a hexyloxygroup, a 2-ethylhexyloxy group, a dodecyloxy group, and a cyclohexyloxygroup), an aryloxy group (an aryloxy group preferably having 6 to 24carbon atoms, and more preferably having 1 to 18 carbon atoms, forexample, a phenoxy group and a naphthyloxy group), an alkylamino group(an alkylamino group preferably having 1 to 36 carbon atoms, and morepreferably having 1 to 18 carbon atoms, for example, a methylaminogroup, an ethylamino group, a propylamino group, a butylamino group, ahexylamino group, a 2-ethylhexylamino group, an isopropylamino group, atert-butylamino group, a tert-octylamino group, a cyclohexylamino group,an N,N-diethylamino group, an N,N-dipropylamino group, anN,N-dibutylamino group, and an N-methyl-N-ethylamino group), anarylamino group (an arylamino group preferably having 6 to 36 carbonatoms, and more preferably having 6 to 18 carbon atoms, for example, aphenylamino group, a naphthylamino group, an N,N-diphenylamino group,and an N-ethyl-N-phenylamino group), or a heterocyclic amino group (aheterocyclic amino group preferably having 1 to 24 carbon atoms, andmore preferably having 1 to 12 carbon atoms, for example, a2-aminopyrrole group, a 3-aminopyrazole group, a 2-aminopyridine group,and a 3-aminopyridine group).

Among the above groups, as R¹¹ and R¹⁶, an alkyl group, an alkenylgroup, an aryl group, a heterocyclic group, an alkylamino group, anarylamino group, and a heterocyclic amino group are preferable, an alkylgroup, an alkenyl group, an aryl group, and a heterocyclic group aremore preferable, an alkyl group, an alkenyl group, and an aryl group arestill more preferable, and an alkyl group is particularly preferable.

In General Formula (8), in the case where the alkyl group, the alkenylgroup, the aryl group, the heterocyclic group, the alkoxy group, thearyloxy group, the alkylamino group, the arylamino group, or theheterocyclic amino group represented by R¹¹ and R¹⁶ is a group which canbe further substituted, the group may be substituted with thesubstituents described in the section of the substituent group A asdescribed above. In the case where the group is substituted with two ormore substituents, these substituents may be the same as or differentfrom each other.

In General Formula (8), X² and X³ each independently represent NR, anitrogen atom, an oxygen atom, or a sulfur atom. Here. R represents ahydrogen atom, an alkyl group (a linear, branched, or cyclic alkyl grouppreferably having 1 to 36 carbon atoms, and more preferably having 1 to12 carbon atoms, for example, a methyl group, an ethyl group, a propylgroup, an isopropyl group, a butyl group, an isobutyl group, atert-butyl group, a hexyl group, a 2-ethylhexyl group, a dodecyl group,a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a1-adamantyl group), an alkenyl group (an alkenyl group preferably having2 to 24 carbon atoms, and more preferably having 2 to 12 carbon atoms,for example, a vinyl group, an allyl group, and a 3-buten-1-yl group),an aryl group (an aryl group preferably having 6 to 36 carbon atoms, andmore preferably having 6 to 18 carbon atoms, for example, a phenyl groupand a naphthyl group), a heterocyclic group (a heterocyclic grouppreferably having 1 to 24 carbon atoms, and more preferably having 1 to12 carbon atoms, for example, a 2-thienyl group, a 4-pyridyl group, a2-furyl group, a 2-pyrimidinyl group, a 1-pyridyl group, a2-benzothiazolyl group, a 1-imidazolyl group, a 1-pyrazolyl group, and abenzotriazol-1-yl group), an acyl group (an acyl group preferably having1 to 24 carbon atoms, and more preferably having 2 to 18 carbon atoms,for example, an acetyl group, a pivaloyl group, a 2-ethylhexyl group, abenzoyl group, and a cyclohexanoyl group), an alkylsulfonyl group (analkylsulfonyl group preferably having 1 to 24 carbon atoms, and morepreferably having 1 to 18 carbon atoms, for example, a methylsulfonylgroup, an ethylsulfonyl group, an isopropylsulfonyl group, and acyclohexylsulfonyl group), and an arylsulfonyl group (an arylsulfonylgroup preferably having 6 to 24 carbon atoms, and more preferably having6 to 18 carbon atoms, for example, a phenylsulfonyl group and anaphthylsulfonyl group).

In General Formula (8), Y¹ and Y² each independently represent NR¹, anitrogen atom, or a carbon atom. R^(c) has the same definition as R ofX² and X³, and the preferred embodiments thereof are also the same.

In General Formula (8), R¹¹ and Y¹ may be bonded to each other to form a5-membered ring (for example, a cyclopentane ring, a pyrrolidine ring, atetrahydrofuran ring, a dioxolane ring, a tetrahydrothiophene ring, apyrrole ring, a furan ring, a thiophene ring, an indole ring, abenzofuran ring, and a benzothiophene ring), a 6-membered ring (forexample, a cyclohexane ring, a piperidine ring, a piperazine ring, amorpholine ring, a tetrahydropyran ring, a dioxane ring, apentamethylene sulfide ring, a dithiane ring, a benzene ring, apyridazine ring, a quinoline ring, and a quinazoline ring), or a7-membered ring (for example, a cycloheptane ring and a hexamethyleneimine ring) together with a carbon atom.

In General Formula (8), R¹⁶ and Y² may be bonded to each other to form a5-membered ring (for example, a cyclopentane ring, a pyrrolidine ring, atetrahydrofuran ring, a dioxolane ring, a tetrahydrothiophene ring, apyrrole ring, a furan ring, a thiophene ring, an indole ring, abenzofuran ring, and a benzothiophene ring), a 6-membered ring (forexample, a cyclohexane ring, a piperidine ring, a piperazine ring, amorpholine ring, a tetrahydropyran ring, a dioxane ring, apentamethylene sulfide ring, a dithiane ring, a benzene ring, apyridazine ring, a quinoline ring, and a quinazoline ring), or a7-membered ring (for example, a cycloheptane ring and ahexamethyleneimine ring) together with a carbon atom.

In General Formula (8), in the case where the 5-, 6-, and 7-memberedrings formed by mutual bonding of R¹¹ and Y¹ as well as R¹⁶ and Y² aresubstitutable rings, the rings may be substituted with the substituentsdescribed in the section of the substituent group A as described above.In the case where the rings are substituted with two or moresubstituents, these substituents may be the same as or different fromeach other.

In General Formula (8), it is preferable that R¹¹ and R¹⁶ are eachindependently a monovalent substituent of which an —Es′ value as asteric parameter is 1.5 or more. The —Es′ value is more preferably 2.0or more, still more preferably 3.5 or more, and particularly preferably5.0 or more.

Here, the —Es′ value as a steric parameter is a parameter whichrepresents steric bulkiness of a substituent. As the value, the —Es′value disclosed in the document (J. A. Macphee, et al, Tetrahedron, Vol.34, pp 3553-3562, and Chemistry Special Edition 107, Structure-activityCorrelation and Drug Design, edited by Toshio Fujita, published on Feb.20, 1986 (Kagaku-Dojin Publishing Company, Inc)) is used.

A preferred embodiment of the compound represented by General Formula(8) is a preferred embodiment in which R¹² to R¹⁵ are each independentlyone in the preferred embodiment cited in the description of R⁵ to R⁸ inGeneral Formula (M), R¹⁷ is one in the preferred embodiment cited in thedescription of R¹⁰ in General Formula (M), Ma is Zn, Cu, Co, or V═O, X²is NR (in which R represents a hydrogen atom or an alkyl group), anitrogen atom, or an oxygen atom. X³ is NR (in which R represents ahydrogen atom or an alkyl group) or an oxygen atom, Y¹ is NR^(c) (inwhich R^(c) represents a hydrogen atom or an alkyl group), a nitrogenatom, or a carbon atom, Y² is a nitrogen atom or a carbon atom, R¹¹ andR¹⁶ are each independently an alkyl group, an aryl group, a heterocyclicgroup, an alkoxy group, or an alkylamino group, X¹ is a group bonded viaan oxygen atom, and a is 0 or 1. R¹¹ and Y¹ may be bonded to each otherto form a 5- or 6-membered ring, or R¹⁶ and Y² may be bonded to eachother to form a 5- or 6-membered ring.

A more preferred embodiment of the compound represented by GeneralFormula (8) is a preferred embodiment in which R¹² to R¹⁵ are eachindependently one in the preferred embodiment cited in the descriptionof R⁵ to R⁸ in the compound represented by General Formula (M), R¹⁷ isone in the preferred embodiment cited in the description of R^(1′) inGeneral Formula (M), Ma is Zn, X² and X³ are each an oxygen atom. Y¹ isNH, Y² is a nitrogen atom, R¹¹ and R¹⁶ are each independently an alkylgroup, an aryl group, a heterocyclic group, an alkoxy group, or analkylamino group, X¹ is a group bonded via an oxygen atom, and a is 0or 1. R¹¹ and Y may be bonded to each other to form a 5- or 6-memberedring, or R¹⁶ and Y² may be bonded to each other to form a 5- or6-membered ring.

From the viewpoint of coloring ability, the molar absorption coefficientof the dipyrromethene metal complex compound represented by GeneralFormulae (7) and (8) is preferably as high as possible. Further, fromthe viewpoint of improving color purity, the maximum absorptionwavelength λmax is preferably 520 nm to 580 nm, and more preferably 530nm to 570 nm. If the value is within the above range, it is possible tomanufacture a color filter having excellent color reproducibility byusing the colored composition of the present invention.

Furthermore, an absorbance at the maximum absorption wavelength (λmax)of the dye compound (A) having a dye structure derived from adipyrromethene dye is preferably 1,000 times or more, more preferably10,000 times or more, and still more preferably 100,000 times or morethe absorbance at 450 nm. If the ratio is within the above range,particularly in the case where a blue color filter is manufactured usingthe colored composition of the present invention, a color filter havinga higher transmittance can be formed. Incidentally, the maximumabsorption wavelength and the molar absorption coefficient are measuredby a spectrophotometer Cary 5 (manufactured by Varian. Inc.).

From the viewpoint of solubility, it is preferable that the meltingpoints of the dipyrromethene metal complex compounds represented byGeneral Formulae (7) and (8) are not too high.

The dipyrromethene metal complex compounds represented by GeneralFormulae (7) and (8) can be synthesized by the methods described in U.S.Pat. Nos. 4,774,339A, 5,433,896A, JP2001-240761A, JP2002-155052A,JP3614586B, Aust. J. Chem., 1965, 11, 1835-1845, J. H. Boger, et al.,Heteroatom Chemistry, Vol. 1, No. 5,389 (1990), and the like.Specifically, the method described in paragraphs “0131” to “0157” ofJP2008-292970A can be applied.

The following (PM-1) to (PM-10) are examples of the dye structure of thedipyrromethene compound, but the present invention is not limitedthereto. In the specific examples, (PM-1) to (PM-10), Zn is a cation.

Furthermore, the following (A-PM-1) to (A-PM-4) are specific examples ofthe dipyrromethene compound, but the present invention is not limitedthereto. Further, polymers containing repeating units derived fromcompounds (A-PM-1, A-PM-3, and A-PM-4) containing a polymerizable groupare also included in the dye compound (A) of the present invention.

In the case where the dye compound which is used in the presentinvention is a xanthene dye, an azo dye, or a squarylium dye (preferablya xanthene dye), a red colored composition can be formed by using acombination of a red colorant (preferably a red pigment) and a yellowcolorant (preferably a yellow pigment). In this case, the mass ratio ofthe dye compound which is used in the present invention to the redand/or yellow colorant is preferably 10:90 to 90:10.

The colored composition of the present invention is used for formationof a colored layer of the color filter. The colored composition used inthe present invention preferably includes, in addition to the dyecompound (A), a curable compound (B), and a solvent (C), and may includeother components.

For example, in the case of forming a colored layer by a photoresist,the colored composition of the present invention is preferably acomposition including a pigment and a photopolymerization initiator, inaddition to the dye compound (A), an alkali-soluble resin as the curablecompound, and a solvent. Further, the colored composition may includecomponents such as a surfactant.

In addition, in the case of forming a colored layer by dry etching, thecolored composition is preferably a composition including a pigment, anda photopolymerization initiator, in addition to the dye compound (A), apolymerizable compound as the curable compound, and a solvent. Further,the colored composition may include components such as a surfactant.

Details thereof will be described below.

<Curable Compound>

The colored composition of the present invention contains a curablecompound. As the curable compound, known polymerizable compounds whichcan be crosslinked by a radical, an acid, or heat can be used. Examplesthereof include polymerizable compounds having an ethylenicallyunsaturated bond, a cyclic ether (epoxy or oxetane), methylol, or thelike. From the viewpoint of sensitivity, the polymerizable compound issuitably selected from compounds having at least one and preferably twoor more terminal ethylenically unsaturated bonds. Among these,polyfunctional polymerizable compounds having 4 or more functionalgroups are preferable, and polyfunctional polymerizable compounds having5 or more functional groups are more preferable.

Such compound groups are widely known in the industrial field of therelevant art and can be used in the present invention without particularlimitation. These may be in any type of chemical forms such as amonomer, a prepolymer, that is, a dimer, a trimer, an oligomer, amixture thereof, and a multimer thereof. The polymerizable compound inthe present invention may be used alone or in combination of two or morekinds thereof.

More specifically, examples of the monomer and prepolymer includeunsaturated carboxylic acids (for example, acrylic acid, methacrylicacid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, andthe like) or esters thereof, amides, and multimers of these, and amongthese, an ester of unsaturated carboxylic acid and an aliphaticpolyhydric alcohol compound, amides of unsaturated carboxylic acid andan aliphatic polyamine compound, and multimers of these are preferable.Moreover, products of an addition reaction between unsaturatedcarboxylic acid esters or amides having nucleophilic substituent such asa hydroxyl group, an amino group, or a mercapto group and monofunctionalor polyfunctional isocyanates or epoxies, products of a dehydrationcondensation reaction between the unsaturated carboxylic acid esters oramides and a monofunctional or polyfunctional carboxylic acid, and thelike are also suitably used. In addition, products of an additionreaction between unsaturated carboxylic acid esters or amides having anelectrophilic substituent such as an isocyanate group or an epoxy groupand monofunctional or polyfunctional alcohols, amines, or thiols, andproducts of a substitution reaction between unsaturated carboxylic acidesters or amides having an eliminatable substituent such as a halogengroup or tosyloxy group and monofunctional or polyfunctional alcohols,amines, or thiols are also suitable. As other examples, instead of theabove unsaturated carboxylic acid, vinyl benzene derivatives ofunsaturated phosphonic acid, styrene, and the like and compound groupssubstituted with vinyl ether, allyl ether, or the like can also be used.

As these specific compounds, the compounds described in paragraph Nos.“0095” to “0108” of JP2009-288705A can also be suitably used in thepresent invention.

Moreover, as the polymerizable compound, a compound which has at leastone addition-polymerizable ethylene group and has an ethylenicallyunsaturated group having a boiling point of 100° C. or higher undernormal pressure is also preferable. Examples of the compound include amonofunctional acrylate or methacrylate such as polyethylene glycolmono(meth)acrylate, polypropylene glycol mono(meth)acrylate, andphenoxyethyl (meth)acrylate; a compound which is obtained by addingethylene oxide or propylene oxide to a polyfunctional alcohol, and then(meth)acrylating the resultant, such as polyethylene glycoldi(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycoldi(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritoltetra(meth)acrylate, dipentaerythritol penta(meth)acrylate,dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate,trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, glycerin, and trimethylolethane, the urethane(meth)acrylates described in JP1973-41708B (JP-S48-41708B), JP1975-6034B(JP-S50-6034B), and JP1976-37193A (JP-S51-37193A), the polyesteracrylates described in JP1973-64183A (JP-S48-64183A), JP1974-43191B(JP-S49-43191B), and JP1977-30490B (JP-S52-30490B), a polyfunctionalacrylate or methacrylate such as epoxy acrylate as a product of areaction between an epoxy resin and a (meth)acrylic acid, and a mixturethereof.

Other examples thereof include a polyfunctional (meth)acrylate which isobtained by reacting a polyfunctional carboxylic acid with a compoundhaving a cyclic ether group such as glycidyl (meth)acrylate, and anethylenically unsaturated group.

Furthermore, as other preferred polymerizable compounds, the compoundshaving a fluorene ring and an ethylenically unsaturated group having 2or more functional groups described in JP2010-160418A, JP2010-129825A.and JP4364216B, and a cardo resin can also be used.

Moreover, as the compound which has a boiling point of 100° C. or higherunder normal pressure and has at least one addition-polymerizableethylenically unsaturated group, compounds described in paragraph Nos.“0254” to “0257” of JP2008-292970A are also suitable.

In addition to those above, radically polymerizable monomers representedby the following General Formulae (MO-1) to (MO-5) can also be suitablyused. Incidentally, in the case where T is an oxyalkylene group in theformulae, the terminal on a carbon atom side binds to R.

R:

T:

Z:

In General Formulae, n is 0 to 14 and m is 1 to 8. A plurality of R'sand T's which are present in one molecule may be the same as ordifferent from each other.

In each of the polymerizable compounds represented by General Formulae(MO-1) to (MO-5), at least one of the plurality of R's represents agroup represented by —OC(═O)CH═CH₂ or —OC(═O)C(CH₃)═CH₂.

As specific examples of the polymerizable compounds represented byGeneral Formulae (MO-1) to (MO-5), the compounds described in paragraphNos. “0248” to “0251” of JP2007-269779A can also be suitably used in thepresent invention.

In addition, a compound which is obtained by adding ethylene oxide orpropylene oxide to the polyfunctional alcohol, which is described asGeneral Formulae (1) and (2) in JP1998-62986A (JP-H10-62986A) togetherwith the specific examples thereof, and then (meth)acrylating theresultant can also be used as a polymerizable compound.

Among these, as the polymerizable compound, dipentaerythritoltriacrylate (KAYARAD D-330 as a commercially available product;manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritoltetraacrylate (KAYARAD D-320 as a commercially available product;manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritolpenta(meth)acrylate (KAYARAD D-310 as a commercially available product;manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritolhexa(meth)acrylate (KAYARAD DPHA as a commercially available product;manufactured by Nippon Kayaku Co., Ltd.), ethyleneoxy-modifieddipentaerythritol hexaacrylate (A-DPH-12E as a commercially availableproduct; manufactured by Shin-Nakamura Chemical Co., Ltd.),pentaerythritol ethoxylate tetraacrylate (KAYARAD RP-1040 as acommercially available product; manufactured by Nippon Kayaku Co.,Ltd.), and a structure in which an ethylene glycol or propylene glycolresidue is interposed between these (meth)acryloyl groups is preferable.Oligomer types of these can also be used.

The polymerizable compound is a polyfunctional monomer and may have anacid group such as a carboxyl group, a sulfonic acid group, and aphosphoric acid group. If an ethylenic compound has an unreactedcarboxyl group as in the case where the ethylene compound is a mixturedescribed above, this compound can be used as is, but if desired, ahydroxyl group of the aforementioned ethylenic compound may be reactedwith a non-aromatic carboxylic anhydride so as to introduce an acidgroup. In this case, specific examples of the non-aromatic carboxylicanhydride used include tetrahydrophthalic anhydride, alkylatedtetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylatedhexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

In the present invention, as a monomer having an acid group, apolyfunctional monomer which is an ester obtained between an aliphaticpolyhydroxy compound and an unsaturated carboxylic acid and provides anacid group by reacting an unreacted hydroxyl group of the aliphaticpolyhydroxy compound with a non-aromatic carboxylic anhydride ispreferable. A monomer in which the aliphatic polyhydroxy compound in theester is pentaerythritol and/or dipentaerythritol is particularlypreferable. Examples of commercially available products thereof includeM-510 and M-520, which are polybasic modified acryl oligomersmanufactured by TOAGOSEI, CO., LTD.

These monomers may be used alone, but since it is difficult to use asingle compound in production, two or more kinds thereof may be used asa mixture. Moreover, if desired, a polyfunctional monomer not having anacid group and a polyfunctional monomer having an acid group may be usedin combination therewith as the monomer.

The acid value of the polyfunctional monomer having an acid group ispreferably 0.1 mgKOH/g to 40 mgKOH/g, and particularly preferably 5mgKOH/g to 30 mgKOH/g. If the acid value of the polyfunctional monomeris too low, the development solubility characteristics deteriorate. Ifthe acid value is too high, difficulty is caused in the production andhandleability, hence a photopolymerization performance deteriorates,which leads to deterioration in curability such as surface smoothness ofpixels. Therefore, in the case where a combination of two or more kindsof polyfunctional monomers having different acid groups is used, or inthe case where a combination of polyfunctional monomers not having anacid group is used, it is preferable to adjust the acid value such thatthe acid value of all the polyfunctional monomers falls within the aboverange.

Furthermore, it is also a preferred embodiment that a polyfunctionalmonomer having a caprolactone structure is contained as a polymerizablecompound.

The polyfunctional monomer having a caprolactone structure is notparticularly limited as long as it has a caprolactone structure in themolecule, and examples thereof include E-caprolactone-modifiedpolyfunctional (meth)acrylates which are obtained by esterifyingpolyhydric alcohols such as trimethylolethane, ditrimethylolethane,trimethylolpropane, ditrimethylolpropane, pentaerythritol,dipentaerythritol, tripentaerythritol, glycerin, diglycerol, andtrimethylolmelamine with (meth)acrylic acid and E-caprolactone. Amongthese, a polyfunctional monomer having a caprolactone structurerepresented by the following General Formula (Z-1) is preferable.

In General Formula (Z-1), all of six R's are each a group represented bythe following General Formula (Z-2). Alternatively, one to five out ofsix R's are a group represented by the following General Formula (Z-2),and the remainder is a group represented by the following GeneralFormula (Z-3).

In General Formula (Z-2), R¹ represents a hydrogen atom or a methylgroup, m represents a number 1 or 2, and “*” represents a direct bond.

In General Formula (Z-3), R¹ represents a hydrogen atom or a methylgroup, and “*” represents a direct bond.

The polyfunctional monomer having such a caprolactone structure iscommercially available from Nippon Kayaku Co., Ltd., as a KAYARAD DPCAseries, and examples thereof include DPCA-20 (a compound in which m=1 inFormulae (Z-1) to (Z-3), the number of the group represented by Formula(Z-2)=2, and all of R¹'s are hydrogen atoms), DPCA-30 (a compound inwhich m=1 in Formulae (Z-1) to (Z-3), the number of the grouprepresented by Formula (Z-2)=3, and all of R¹'s are hydrogen atoms),DPCA-60 (a compound in which m=1 in Formulae (Z-1) to (Z-3), the numberof the group represented by Formula (Z-2)=6, and all of R¹'s arehydrogen atoms), and DPCA-120 (a compound in which m=2 in Formulae (Z-1)to (Z-3), the number of the group represented by Formula (Z-2)=6, andall of R¹'s are hydrogen atoms).

In the present invention, the polyfunctional monomer having acaprolactone structure can be used alone or as a mixture of two or morekinds thereof.

Moreover, the specific monomer in the present invention is preferably atleast one kind selected from a group of compounds represented by thefollowing General Formula (Z-4) or (Z-5).

In General Formulae (Z-4) and (Z-5), E's each independently represent—((CH₂)_(y)CH₂O)— or —((CH₂)_(y)CH(CH₃)O)—, y's each independentlyrepresent an integer of 0 to 10, and X's each independently represent anacryloyl group, a methacryloyl group, a hydrogen atom, or a carboxylgroup.

In General Formula (Z-4), the sum of the acryloyl group and themethacryloyl group is 3 or 4, m's each independently represent aninteger of 0 to 10, and the sum of the respective m's is an integer of 0to 40. Here, in the case where the sum of the respective m's is 0, anyone of X's is a carboxyl group.

In General Formula (Z-5), the sum of the acryloyl group and themethacryloyl group is 5 or 6, n's each independently represent aninteger of 0 to 10, and the sum of the respective n's is an integer of 0to 60. Here, in the case where the sum of the respective n's is 0, oneof X's is a carboxyl group.

In General Formula (Z-4), m is preferably an integer of 0 to 6, and morepreferably an integer of 0 to 4.

Moreover, the sum of the respective m's is preferably an integer of 2 to40, more preferably an integer of 2 to 16, and particularly preferablyan integer of 4 to 8.

In General Formula (Z-5), n is preferably an integer of 0 to 6, and morepreferably an integer of 0 to 4.

Furthermore, the sum of the respective n's is preferably an integer of 3to 60, more preferably an integer of 3 to 24, and particularlypreferably an integer of 6 to 12.

In addition, —((CH₂)_(y)CH₂O)— or —((CH₂)_(y)CH(CH₃)O)— in GeneralFormula (Z-4) or (Z-5) is preferably in the form in which the terminalon an oxygen atom side binds to X.

The compound represented by General Formula (Z-4) or (Z-5) may be usedalone or in combination of two or more kinds thereof. In particular, aform in which all of six X's in General Formula (Z-5) are an acryloylgroup is preferable.

Moreover, the total content of the compound represented by GeneralFormula (Z-4) or (Z-5) in the polymerizable compound is preferably 20%by mass or more, and more preferably 50% by mass or more.

The compound represented by General Formula (Z-4) or (Z-5) can besynthesized by steps known in the related art, which includes a step ofbonding ethylene oxide or propylene oxide to pentaerythritol ordipentaerythritol by a ring-opening addition reaction to form aring-opening skeleton, and a step of reacting, for example,(meth)acryloyl chloride to a terminal hydroxyl group of the ring-openingskeleton to introduce a (meth)acryloyl group. Since the respective stepsare well-known, a person skilled in the art can easily synthesize thecompound represented by General Formula (Z-4) or (Z-5).

Among the compounds represented by General Formula (Z-4) or (Z-5), apentaerythritol derivative and/or a dipentaerythritol derivative is/aremore preferable.

Specific examples of the compounds include compounds represented by thefollowing Formulae (a) to (f) (hereinafter also referred to as“exemplary compounds (a) to (f)”). Among these, the exemplary compounds(a), (b), (e), and (f) are preferable.

Examples of commercially available products of the polymerizablecompounds represented by General Formulae (Z-4) and (Z-5) include SR-494which is a tetrafunctional acrylate having four ethyleneoxy chains,manufactured by Sartomer Company, Inc., and DPCA-60 which is ahexafunctional acrylate having six pentyleneoxy chains and TPA-330 whichis a trifunctional acrylate having three isobutyleneoxy chains,manufactured by Nippon Kayaku Co., Ltd.

Moreover, as the polymerizable compounds, the urethane acrylatesdescribed in JP1973-41708B (JP-S48-41708B), JP1976-37193A(JP-S51-37193A), JP1990-32293B (JP-H02-32293B), and JP1990-16765B(JP-H02-16765B) or urethane compounds having an ethylene oxide-basedskeleton described in JP1983-49860B (JP-S58-49860B), JP1981-17654B(JP-S56-17654B), JP1987-39417B (JP-S62-39417B), and JP1987-39418B(JP-S62-39418B) are also preferable. Furthermore, ifaddition-polymerizable compounds, which have an amino structure or asulfide structure in a molecule and are described in JP1988-277653A(JP-S63-277653A), JP1988-260909A (JP-S63-260909A), and JP1989-105238A(JP-H01-105238A), are used as the polymerizable compounds, a curablecomposition which is extremely excellent in photosensitization speed canbe obtained.

Examples of commercially available products of the polymerizablecompounds include urethane oligomers UAS-10 and UAB-140 (manufactured bySanyo-Kokusaku Pulp, Co., Ltd.), UA-7200 (manufactured by SHIN-NAKAMURACHEMICAL CO., LTD.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.),and UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufacturedby KYOEISHA CHEMICAL Co., Ltd.).

As the cyclic ether (epoxy or oxethane), examples of a bisphenol A typeepoxy resin, which have an epoxy group, include JER-827, JER-828,JER-834, JER-1001, JER-1002, JER-1003, JER-1055, JER-1007, JER-1009, andJER-1010 (all manufactured by Japan Epoxy Resins Co., Ltd.), and EPICLON840, EPICLON 860, EPICLON 1050, EPICLON 1051, and EPICLON 1055 (allmanufactured by DIC Corporation); examples of a bisphenol F type epoxyresin include JER-806, JER-807. JER-4004, JER-4005, JER-4007, andJER-4010 (all manufactured by Japan Epoxy Resins Co., Ltd.), EPICLON 830and EPICLON 835 (both manufactured by DIC Corporation), and LCE-21 andRE-602S (all manufactured by Nippon Kayaku Co., Ltd.); examples of aphenol novolac type epoxy resin include JER-152, JER-154, JER-157S70,and JER-157S65 (all manufactured by Japan Epoxy Resins Co., Ltd.), andEPICLON N-740, EPICLON N-770, and EPICLON N-775 (all manufactured by DICCorporation); examples of a cresol novolac type epoxy resin includeEPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLONN-680, EPICLON N-690, and EPICLON N-695 (all manufactured by DICCorporation), EPICLON HP-7200 (manufactured by DIC Corporation), andEOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.); and examples of analiphatic epoxy resin include ADEKA RESIN EP-4080S. ADEKA RESINEP-4085S. and ADEKA RESIN EP-4088S (all manufactured by ADEKACORPORATION), CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE2085. EHPE-3150 (a 1,2-epoxy-4-(2-oxylanyl(cyclohexane adduct of2,2-bis(hydroxymethyl)-1-butanol). EPOLEAD PB 3600, and EPOLEAD PB 4700(all manufactured by Daicel Corporation), DENACOL EX-211L, EX-212L,EX-214L, EX-216L, EX-321L, and EX-850L (all manufactured by NagaseChemteX Corporation), ADEKA RESIN EP-4000S. ADEKA RESIN EP-4003S, ADEKARESIN EP-4010S, and ADEKA RESIN EP-4011S (all manufactured by ADEKACORPORATION). NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, and EPPN-502(all manufactured by ADEKA CORPORATION), and JER-1031S (manufactured byJapan Epoxy Resins Co., Ltd.). Such polymerizable compounds are suitablefor a case of forming a pattern by a dry etching method.

Details of how to use these polymerizable compounds, such as thestructure, whether the polymerizable compounds are used singly or usedin combination thereof, and the amount of the polymerizable compoundsadded, can be arbitrarily set according to the designed finalperformance of the colored composition. For example, from the viewpointof sensitivity, a structure in which the content of an unsaturated groupper molecule is large is preferable, and in many cases, it is preferablethat the polymerizable compound has 2 or more functional groups.Moreover, from the viewpoint of enhancing the strength of a cured filmformed of the colored composition, it is preferable that thepolymerizable compound has 3 or more functional groups. In addition, amethod for adjusting both the sensitivity and the strength by usingcompounds which differ in the number of functional groups and havedifferent polymerizable groups (for example, an acrylic acid ester, amethacrylic acid ester, a styrene-based compound, and a vinylether-basedcompound) in combination with the other components is also effective.Further, it is preferable to use polymerizable compounds having 3 ormore functional groups and differing in the length of an ethylene oxidechain in combination with the other components since the developabilityof the colored composition can be adjusted, and excellent patternformability is obtained.

In addition, from the viewpoints of the compatibility with othercomponents (for example, a photopolymerization initiator, a substance tobe dispersed, and an alkali-soluble resin) contained in the coloredcomposition, and the dispersibility, how to select and use thepolymerizable compound is an important factor. For example, if alow-purity compound is used or a combination of two or more kindsthereof is used, the compatibility can be improved in some cases. Inaddition, there are also cases where specific structures are selectedfrom the viewpoint of improving the adhesiveness to a hard surface of asupport or the like.

In the case where the polymerizable compound is blended into the coloredcomposition of the present invention, the content of the polymerizablecompound is preferably 5% by mass to 40% by mass, more preferably 7% bymass to 35% by mass, and particularly preferably 8% by mass to 30% bymass, with respect to the total solid contents of the coloredcomposition. The composition of the present invention may contain onekind or two or more kinds of polymerizable compound. In the case wherethe composition contains two or more kinds of the polymerizablecompound, the total amount thereof is preferably within the above range.

<Polyfunctional Thiol Compound>

The colored composition of the present invention may containpolyfunctional thiol compounds having two or more mercapto groups in themolecule for the purpose of promoting the reaction of the polymerizablecompounds. The polyfunctional thiol compounds are preferably secondaryalkanethiols, and particularly preferably compounds having structuresrepresented by the following General Formula (I).

In General Formula (I), n represents an integer of 2 to 4. L¹ representsa divalent to tetravalent linking group, and L² represents a single bondor a divalent linking group.

L¹ is preferably an aliphatic group having 2 to 12 carbon atoms, or agroup formed by combination of an aliphatic group having 2 to 12 carbonatoms and a heterocyclic group. The heterocyclic group may be monocyclicor polycyclic, is preferably monocyclic. The heterocyclic grouppreferably contains a nitrogen atom as a hetero atom.

In the case where L² represents a divalent linking group, an alkylenegroup having 1 to 3 carbon atoms is preferable, and a methylene group ismore preferable.

Specific examples of the polyfunctional thiol compound include thefollowing compounds.

The content of the polyfunctional thiol compound in the coloredcomposition of the present invention is preferably 0.01% by mass to 8.9%by mass, and more preferably 0.1% by mass to 6.4% by mass, with respectto the total solid content excluding the solvent. The polyfunctionalthiol may be used alone or in combination of two or more kinds thereof.In the case where the colored composition contains two or more kinds ofpolyfunctional thiol compound, the total amount is preferably within theabove range.

<Solvent>

The colored composition of the present invention contains an organicsolvent.

Basically, the organic solvent is not particularly limited as long asthe solvent satisfies the solubility of the respective components or thecoatability of the colored composition. In particular, it is preferableto select the organic solvent in consideration of the solubility,coatability, and safety of an ultraviolet absorber, the alkali-solubleresin, the dispersant, or the like. In addition, when the coloredcomposition in the present invention is prepared, the compositionpreferably includes at least two kinds of organic solvents.

Suitable examples of the organic solvent include esters such as ethylacetate, n-butyl acetate, isobutyl acetate, butyl propionate, isopropylbutyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate,alkyl oxyacetate (for example, methyl oxyacetate, ethyl oxyacetate, andbutyl oxyacetate (for example, methyl methoxyacetate, ethylmethoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethylethoxyacetate)), alkyl 3-oxypropionate esters (for example, methyl3-oxypropionate and ethyl 3-oxypropionate (for example, methyl3-methoxypropionate, ethyl 3-methoxypropionate, methyl3-ethoxypropionate, and ethyl 3-ethoxypropionate)), alkyl2-oxypropionate esters (for example, methyl 2-oxypropionate, ethyl2-oxypropionate, or propyl 2-oxypropionate (for example, methyl2-methoxypropionate, ethyl 2-methoxypropionate, propyl2-methoxypropionate, methyl 2-ethoxypropionate, or ethyl2-ethoxypropionate)), methyl 2-oxy-2-methyl propionate and ethyl2-oxy-2-methyl propionate (for example, methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methyl propionate), methyl pyruvate,ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethylacetoacetate, methyl 2-oxobutanoate, and ethyl 2-oxobutanoate; etherssuch as diethylene glycol dimethyl ether, tetrahydrofuran, ethyleneglycol monomethyl ether, ethylene glycol monoethyl ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycolmonomethyl ether, diethylene glycol monoethyl ether, diethylene glycolmonobutyl ether, propylene glycol monomethyl ether, propylene glycolmonomethyl ether acetate, propylene glycol monoethyl ether acetate, andpropylene glycol monopropyl ether acetate; ketones such as methyl ethylketone, cyclohexanone, 2-heptanone, 3-heptanone, and cyclopentanone; andaromatic hydrocarbons such as toluene and xylene.

From the viewpoint of the solubility of an ultraviolet absorber and thealkali-soluble resin, and improvement of the shape of the coatedsurface, it is also preferable to mix two or more kinds of these organicsolvents. In this case, a mixed solution consisting of two or more kindsselected from the aforementioned methyl 3-ethoxypropionate, ethyl3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethyleneglycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate,2-heptanone, cyclohexanone, ethylcarbitol acetate, butylcarbitolacetate, propylene glycol methyl ether, and propylene glycol methylether acetate is particularly preferable.

From the viewpoint of coatability, the content of the organic solvent inthe colored composition is set such that the concentration of the totalsolid contents of the composition becomes preferably 5% by mass to 80%by mass, more preferably 5% by mass to 60% by mass, and particularlypreferably 10% by mass to 50% by mass.

The composition of the present invention may include one kind or two ormore kinds of organic solvent. In the case where the compositionincludes two or more kinds of organic solvent, the total amount thereofis preferably within the above range.

<Pigment>

It is preferable that the colored composition of the present inventionfurther includes a pigment, and more preferably includes a pigmenthaving a phthalocyanine skeleton.

As the pigment used in the present invention, various inorganic ororganic pigments known in the related art can be used, and organicpigments are preferably used. As the pigment, one having a hightransmittance is preferable.

Examples of the inorganic pigment include black pigments such as carbonblack and titanium black, metal compounds represented by a metal oxide,a metal complex salt, or the like, and specific examples thereof includemetal oxides of iron, cobalt, aluminum, cadmium, lead, copper, titanium,magnesium, chromium, zinc, antimony, and the like, and complex oxides ofmetals.

Examples of the organic pigment include:

-   -   C. I. Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110,        138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;    -   C. I. Pigment Orange 36, 38, 43, 71;    -   C. I. Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176,        177, 179, 209, 220, 224, 242, 254, 255, 264, 270;    -   C. I. Pigment Violet 19, 23, 32, 39;    -   C. I. Pigment Blue 1, 2, 15, 15:1, 15:3, 15:6, 16, 22, 60, 66;    -   C. I. Pigment Green 7, 36, 37, 58;    -   C. I. Pigment Brown 25, 28; and    -   C. I. Pigment Black 1.

Examples of the pigment which can be preferably used in the presentinvention include the following ones, but the present invention is notlimited thereto.

-   -   C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151,        154, 167, 180, 185,    -   C. I. Pigment Orange 36, 71.    -   C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254,        255, 264,    -   C. I. Pigment Violet 19, 23, 32,    -   C. I. Pigment Blue 15:1, 15:3, 15:6, 16, 22, 60, 66.    -   C. I. Pigment Green 7, 36, 37, 58, and    -   C. I. Pigment Black 1.

These organic pigments can be used alone or in various combinations foradjustment of spectrum or improvement of color purity. Specific examplesof the combination are shown below. For example, as a red pigment, ananthraquinone-based pigment, a perylene-based pigment, or adiketopyrrolopyrrole-based pigment can be used alone or as a mixture ofat least one kind of these with a disazo-based yellow pigment, anisoindoline-based yellow pigment, a quinophthalone-based yellow pigment,or a perylene-based red pigment. Examples of the anthraquinone-basedpigment include C. I. Pigment Red 177, examples of the perylene-basedpigment include C. I. Pigment Red 155, and C. I. Pigment Red 224, andexamples of the diketopyrrolopyrrole-based pigment include C. I. PigmentRed 254. In view of chromatic resolving properties, a mixture of theabove pigment with C. I. Pigment Yellow 139 is preferable. The massratio between the red pigment and the yellow pigment is preferably 100:5to 100:50. If the mass ratio is 100:4 or less, it is difficult to reducethe light transmittance at 400 nm to 500 nm, and if it is 100:51 ormore, a dominant wavelength moves closer to a short wavelength, so acolor separating power cannot be improved in some cases. In particular,the mass ratio is optimally in a range of 100:10 to 100:30. Moreover, inthe case of a combination of red pigments, the mass ratio can beadjusted according to the required spectrum.

In addition, as a green pigment, a halogenated phthalocyanine-basedpigment can be used alone or as a mixture of this pigment with adisazo-based yellow pigment, a quinophthalone-based yellow pigment, anazomethine-based yellow pigment, or an isoindoline-based yellow pigment.As an example of such pigments, a mixture of C. I. Pigment Green 7, 36,or 37 with C. I. Pigment Yellow 83, C. I. Pigment Yellow 138, C. I.Pigment Yellow 139, C. I. Pigment Yellow 150, C. I. Pigment Yellow 180,or C. I. Pigment Yellow 185 is preferable. The mass ratio between thegreen pigment and the yellow pigment is preferably 100:5 to 100:150. Themass ratio is particularly preferably in a range of 100:30 to 100:120.

As a blue pigment, a phthalocyanine-based pigment can be used alone oras a mixture of this pigment with a dioxazine-based violet pigment. Forexample, a mixture of C. I. Pigment Blue 15:6 with C. I. Pigment Violet23 is preferable. The mass ratio between the blue pigment and the violetpigment is preferably 100:0 to 100:100 and more preferably 100:10 orless.

Moreover, as a pigment for a black matrix, carbon, titanium black, ironoxide, or titanium oxide may be used alone or as a mixture, and acombination of carbon with titanium black is preferable. The mass ratiobetween carbon and titanium black is preferably in a range of 100:0 to100:60.

It is preferable to blend a pigment in other color than black into thecolored composition of the present invention, with a blue pigment beingpreferable.

In the case where the pigment is used for a color filter, the primaryparticle size of the pigment is preferably 100 nm or less from theviewpoint of color unevenness or contrast. From the viewpoint ofdispersion stability, the primary particle size is preferably 5 nm ormore. The primary particle size of the pigment is more preferably 5 nmto 75 nm, still more preferably 5 nm to 55 nm, and particularlypreferably 5 nm to 35 nm.

The primary particle size of the pigment can be measured by a knownmethod such as electron microscopy.

Among these, the pigment is preferably a pigment selected from ananthraquinone pigment, a diketopyrrolopyrrole pigment, a phthalocyaninepigment, a quinophthalone pigment, an isoindoline pigment, an azomethinepigment, and a dioxazine pigment. In particular, C. I. Pigment Red 177(anthraquinone pigment), C. I. Pigment Red 254 (diketopyrrolopyrrolepigment), C. I. Pigment Green 7, 36, 58. C. I. Pigment Blue 15:6(phthalocyanine pigment), C. I. Pigment Yellow 138 (quinophthalonepigment). C. I. Pigment Yellow 139, 185 (isoindoline pigments), C. I.Pigment Yellow 150 (azomethine pigment), and C. I. Pigment Violet 23(dioxazine pigment) are most preferable.

In the case where a pigment is blended into the colored composition ofthe present invention, the content of the pigment is preferably 10% bymass to 70% by mass, more preferably 20% by mass to 60% by mass, andstill more preferably 25% by mass to 50% by mass, with respect to thetotal amount of components excluding a solvent, contained in the coloredcomposition.

The composition of the present invention may contain one kind or two ormore kinds of pigment. In the case where the composition contains two ormore kinds, the total amount thereof is preferably within the aboverange.

The colored composition of the present invention may include known dyes.For example, the dyes disclosed in JP1989-90403A (JP-S64-90403A),JP1989-91102A (JP-S64-91102A), JP1989-94301A (JP-H01-94301A),JP1994-11614A (JP-H06-11614A), JP2592207B, U.S. Pat. Nos. 4,808,501A,5,667,920A, 505,950A, 5,667,920A. JP1993-333207A (JP-H05-333207A),JP1994-35183A (JP-H06-35183A), JP1994-51115A (JP-H06-51115A), andJP1994-194828A (JP-H06-194828A) can be used. With respect to thechemical structure, dyes such as a pyrazoleazo based-dye, a pyrromethenebased-dye, an anilinoazo based-dye, a triphenylmethane based-dye, ananthraquinone based-dye, a benzylidene based-dye, an oxonol based-dye, apyrazoletriazole azo based-dye, a pyridoneazo based-dye, a cyaninebased-dye, a phenothiazine based-dye, and apyrrolopyrazoleazomethine-based dye can be used.

In addition, a dye multimer may also be used as the dye. Examples of thedye multimer include the compounds described in JP2011-213925A,JP2013-041097A, and the like.

<Photopolymerization Initiator>

From the viewpoint of further improving sensitivity, it is preferablethat the colored composition of the present invention contains aphotopolymerization initiator.

The photopolymerization initiator is not particularly limited as long asthe photopolymerization initiator has an ability of initiatingpolymerization of the polymerizable compound, and can be appropriatelyselected from known photopolymerization initiators. For example,photopolymerization initiators sensitive to light rays in a range fromthe ultraviolet region to visible light are preferable. In addition, thephotopolymerization initiator may be either an activator which interactswith a photo-excited sensitizer in any way and generates active radicalsor an initiator which initiates cationic polymerization according to thetype of monomer.

Furthermore, it is preferable that the photopolymerization initiatorcontains at least one kind of compound having at least a molarabsorption coefficient of about 50 in a range of about 300 nm to 800 nm(more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenatedhydrocarbon derivatives (for example, a derivative having a triazineskeleton, and a derivative having an oxadiazole skeleton), acylphosphine compounds such as acyl phosphine oxide, oxime compounds suchas hexaaryl biimidazole and oxime derivatives, organic peroxides, thiocompounds, ketone compounds, aromatic onium salts, ketoxime ethers,aminoacetophenone compounds, and hydroxyacetophenone, among which oximecompounds are preferable.

Furthermore, from the viewpoint of exposure sensitivity, the compound ispreferably a compound selected from a group consisting of atrihalomethyl triazine compound, a benzyl dimethyl ketal compound, anα-hydroxyketone compound, an α-aminoketone compound, an acyl phosphinecompound, a phosphine oxide compound, a metallocene compound, an oximecompound, a triarylimidazole dimer, an onium compound, a benzothiazolecompound, a benzophenone compound, an acetophenone compound and aderivative thereof, a cyclopentadiene-benzene-iron complex and a saltthereof, a halomethyl oxadiazole compound, and a 3-aryl-substitutedcoumarin compound.

The compound is more preferably a trihalomethyl triazine compound, anα-aminoketone compound, an acyl phosphine compound, a phosphine oxidecompound, an oxime compound, a triallylimidazole dimer, atriarylimidazole compound, a benzoimidazole compound, an onium compound,a benzophenone compound, or an acetophenone compound, and particularlypreferably at least one kind of compound selected from a groupconsisting of a trihalomethyl triazine compound, an α-aminoketonecompound, an oxime compound, a triallylimidazole compound, abenzophenone compound, a triarylimidazole compound, and a benzoimidazolecompound, Further, the triarylimidazole compound may be a mixturethereof with benzoimidazole.

Specifically, the trihalomethyltriazine compound is exemplified asfollows. Incidentally, Ph is a phenyl group.

As the triarylimidazole compound and the benzoimidazole compound, thefollowing compounds are exemplified.

As the trihalomethyltriazine compound, a commercially available productcan also be used, and for example, TAZ-107 (manufactured by MidoriKagaku Co., Ltd.) can also be used.

Particularly, in the case where the colored composition of the presentinvention is used for the manufacture of a color filter included in asolid-state imaging element, a fine pattern needs to be formed in asharp shape. Accordingly, it is important that the composition hascurability and is developed without residues in an unexposed area. Fromthis viewpoint, it is particularly preferable to use an oxime compoundas a polymerization initiator. In particular, in the case where a finepattern is formed in the solid-state imaging element, stepper exposureis used for exposure for curing. However, the exposure machine used atthis time is damaged by halogen in some cases, so it is necessary toreduce the amount of a polymerization initiator added. In considerationof this point, in order to form a fine pattern as in a solid-stateimaging element, it is particularly preferable to use an oxime compoundas the photopolymerization initiator (D).

Examples of the halogenated hydrocarbon compound having a triazineskeleton include the compounds described in Wakabayashi, et al., Bull.Chem. Soc. Japan, 42, 2924 (1969), the compounds described inUK1388492B, the compounds described in JP1978-133428A (JP-S53-133428A),the compounds described in GE3337024B, the compound described in F. C.Schaefer, et al., J. Org. Chem.; 29, 1527 (1964), the compoundsdescribed in JP1987-58241A (JP-S62-58241A), the compounds described inJP1993-281728A (JP-H05-281728A), the compounds described inJP1993-34920A (JP-H05-34920A), and the compounds described in U.S. Pat.No. 4,212,976A, in particular, the compounds described in paragraph No.“0075” of JP2013-077009A.

In addition, as photopolymerization initiators other than those above,acridine derivatives are exemplified. Specific examples thereof includethe compound described in paragraph No. “0076” of JP2013-077009A, thecontents of which are incorporated herein.

Examples of the ketone compound include the compound described inparagraph No. “0077” of JP2013-077009A, the contents of which areincorporated herein.

As the photopolymerization initiator, a hydroxyacetophenone compound, anaminoacetophenone compound, and an acyl phosphine compound can also besuitably used. More specifically, for example, theaminoacetophenone-based initiator described in JP1998-291969A(JP-H10-291969A), and the acyl phosphine oxide-based initiator describedin JP4225898B can also be used.

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173,IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (product names, allmanufactured by BASF) can be used. As the aminoacetophenone-basedinitiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (product names,all manufactured by BASF) which are commercially available products canbe used. In addition, as the aminoacetophenone-based initiator, thecompound described in JP2009-191179A, of which an absorption wavelengthmatches a light source with a long wavelength of 365 nm, 405 nm, or thelike can be used. Moreover, as the acyl phosphine-based initiator,IRGACURE-819 or DAROCUR-TPO (product names, both manufactured by BASF)which are commercially available products can be used.

Examples of the photopolymerization initiator more preferably includeoxime compounds. As specific examples of the oxime compounds, thecompound described in JP2001-233842A, the compound described inJP2000-80068A, or the compound described in JP2006-342166A can be used.

Examples of the oxime compound such as an oxime derivative, which issuitably used as the photopolymerization initiator in the presentinvention, include 3-benzoyloxyiminobutan-2-one,3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one,2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one,2-benzoyloxyimino-1-phenylpropan-1-one,3-(4-toluenesulfonyloxy)iminobutan-2-one, and2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

Examples of the oxime compound include the compounds described in J. C.S. Perkin II (1979), pp. 1653-1660, J. C. S. Perkin II (1979), pp.156-162, Journal of Photopolymer Science and Technology (1995), pp.202-232, and JP2000-66385A; and the compounds described respectively inJP2000-80068A, JP2004-534797A, and JP2006-342166A.

As the commercially available product, IRGACURE-OXE01 (manufactured byBASF) and IRGACURE-OXE02 (manufactured by BASF) are also suitably used.

In addition, commercially available products such as TRONLY TR-PBG-304,TRONLY TR-PBG-309, and TRONLY TR-PBG-305 (all manufactured by CHANGZHOUTRONLY NEW ELECTRONIC MATERIALS CO., LTD.), and ADEKA ARKLS NCI-831 andADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also beused.

Furthermore, as oxime compounds other than those as described above, thecompound described in JP2009-519904A in which oxime is linked to anN-position of carbazole, the compound described in U.S. Pat. No.7,626,957B in which a hetero-substituent is introduced into abenzophenone site, the compounds described in JP2010-15025A andUS2009/292039A in which a nitro group is introduced into a dyestructure, the ketoxime compound described in WO2009/131189A, thecompound described in U.S. Pat. No. 7,556,910B which contains a triazineskeleton and an oxime skeleton in the same molecule, the compounddescribed in JP2009-221114A, which has maximum absorption at 405 nm andhas excellent sensitivity to a g-ray light source, and the like may beused.

The cyclic oxime compounds described in JP2007-231000A andJP2007-322744A can also be suitably used. Among the cyclic oximecompounds, the cyclic oxime compounds ring-fused to a carbazole dye,which are described in JP2010-32985A and JP2010-185072A, are preferablefrom the viewpoint of high sensitivity since these compounds have highlight absorptivity.

Furthermore, the compound described in JP2009-242469A, which is an oximecompound having an unsaturated bond in a specific moiety, can also besuitably used since this compound makes it possible to improvesensitivity by reproducing active radicals from polymerization-inactiveradicals.

Particularly preferred examples of the oxime compounds include the oximecompound having a specific substituent described in JP2007-269779A andthe oxime compound having a thioaryl group described in JP2009-191061A.

Specifically, the oxime compound which is a photopolymerizationinitiator is preferably a compound represented by the following GeneralFormula (OX-1). Incidentally, the compound may be an oxime compound inwhich an N—O bond of oxime forms an (E) isomer, an oxime compound inwhich the N—O bond forms a (Z) isomer, or a mixture in which the N—Obonds form a mixture of an (E) isomer and a (Z) isomer.

In General Formula (OX-1), R and B each independently represent amonovalent substituent, A represents a divalent organic group, and Arrepresents an aryl group.

In General Formula (OX-1), the monovalent substituent represented by Ris preferably a monovalent non-metal atomic group.

Examples of the monovalent non-metal atomic group include an alkylgroup, an aryl group, an acyl group, an alkoxycarbonyl group, anaryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group,and an arylthiocarbonyl group. Further, these groups may have one ormore substituents. Moreover, the above substituents may further besubstituted with other substituents.

Examples of the substituents include a halogen atom, an aryloxy group,an alkoxycarbonyl or aryloxycarbonyl group, an acyloxy group, an acylgroup, an alkyl group, and an aryl group.

The alkyl group is preferably an alkyl group having 1 to 30 carbonatoms, and specific examples thereof include a methyl group, an ethylgroup, a propyl group, a butyl group, a hexyl group, an octyl group, adecyl group, a dodecyl group, an octadecyl group, an isopropyl group, anisobutyl group, a sec-butyl group, a tert-butyl group, a 1-ethylpentylgroup, a cyclopentyl group, a cyclohexyl group, a trifluoromethyl group,a 2-ethylhexyl group, a phenacyl group, a 1-naphthoylmethyl group, a2-naphthoylmethyl group, a 4-methylsulfanylphenacyl group,4-phenylsulfanylphenacyl group, a 4-dimethylaminophenacyl group, a4-cyanophenacyl group, a 4-methylphenacyl group, a 2-methylphenacylgroup, a 3-fluorophenacyl group, a 3-trifluoromethylphenacyl group, anda 3-nitrophenacyl group.

The aryl group is preferably an aryl group having 6 to 30 carbon atoms,and specific examples thereof include a phenyl group, a biphenyl group,a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a9-phenanthryl group, a 1-pyrenyl group, a 5-naphthacenyl group, a1-indenyl group, a 2-azulenyl group, a 9-fluorenyl group, a terphenylgroup, an octaphenyl group, an o-tolyl group, an m-tolyl group, ap-tolyl group, a xylyl group, an o-cumenyl group, an m-cumenyl group, ap-cumenyl group, a mesityl group, a pentalenyl group, a binaphthalenylgroup, a ternaphthalenyl group, a quaternaphthalenyl group, a heptalenylgroup, a biphenylenyl group, an indacenyl group, a fluoranthenyl group,an acenaphthylenyl group, an aceanthrylenyl group, a phenalenyl group, afluorenyl group, an anthryl group, a bianthracenyl group, ateranthracenyl group, a quateranthracenyl group, an anthraquinolylgroup, a phenanthryl group, a triphenylenyl group, a pyrenyl group, achrysenyl group, a naphthacenyl group, a pleiadenyl group, a picenylgroup, a perylenyl group, a pentaphenyl group, a pentacenyl group, atetraphenylenyl group, a hexaphenyl group, a hexacenyl group, arubicenyl group, a coronenyl group, a trinaphthylenyl group, aheptaphenyl group, a heptacenyl group, a pyranthrenyl group, and anovalenyl group.

The acyl group is preferably an acyl group having 2 to 20 carbon atoms,and specific examples thereof include an acetyl group, a propanoylgroup, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, abenzoyl group, a 1-naphthoyl group, a 2-naphthoyl group, a4-methylsulfanylbenzoyl group, a 4-phenylsulfanylbenzoyl group, a4-dimethylaminobenzoyl group, a 4-diethylaminobenzoyl group, a2-chlorobenzoyl group, a 2-methylbenzoyl group, a 2-methoxybenzoylgroup, a 2-butoxybenzoyl group, a 3-chlorobenzoyl group, a3-trifluoromethylbenzoyl group, a 3-cyanobenzoyl group, a 3-nitrobenzoylgroup, a 4-fluorobenzoyl group, a 4-cyanobenzoyl group, and a4-methoxybenzoyl group.

The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2to 20 carbon atoms, and specific examples thereof include amethoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group,a butoxycarbonyl group, a hexyloxycarbonyl group, an octyloxycarbonylgroup, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and atrifluoromethyloxycarbonyl group.

Specific examples of the aryloxycarbonyl group include a phenoxycarbonylgroup, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a4-methylsulfanylphenyloxycarbonyl group, a4-phenylsulfanylphenyloxycarbonyl group, a4-dimethylaminophenyloxycarbonyl group, a4-diethylaminophenyloxycarbonyl group, a 2-chlorophenyloxycarbonylgroup, a 2-methylphenyloxycarbonyl group, a 2-methoxyphenyloxycarbonylgroup, a 2-butoxyphenyloxycarbonyl group, a 3-chlorophenyloxycarbonylgroup, a 3-trifluoromethylphenyloxycarbonyl group, a3-cyanophenyloxycarbonyl group, a 3-nitrophenyloxycarbonyl group, a4-fluorophenyloxycarbonyl group, a 4-cyanophenyloxycarbonyl group, and a4-methoxyphenyloxycarbonyl group.

As the heterocyclic group, an aromatic or aliphatic heterocycle having anitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom ispreferable.

Specific examples of the heterocyclic group include a thienyl group, abenzo[b]thienyl group, a naphtho[2,3-b]thienyl group, a thianthrenylgroup, a furyl group, a pyranyl group, an isobenzofuranyl group, achromenyl group, a xanthenyl group, a phenoxathiinyl group, a2H-pyrrolyl group, a pyrrolyl group, an imidazolyl group, a pyrazolylgroup, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, apyridazinyl group, an indolizinyl group, an isoindolyl group, a3H-indolyl group, an indolyl group, a 1H-indazolyl group, a purinylgroup, a 4H-quinolizinyl group, an isoquinolyl group, a quinolyl group,a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, aquinazolinyl group, a cinnolinyl group, a pteridinyl group, a4aH-carbazolyl group, a carbazolyl group, a β-carbolinyl group, aphenanthrydinyl group, an acridinyl group, a perimidinyl group, aphenanthrolinyl group, a phenazinyl group, a phenarsazinyl group, anisothiazolyl group, a phenothiazinyl group, an isoxazolyl group, afurazanyl group, a phenoxazinyl group, an isochromanyl group, achromanyl group, a pyrrolidinyl group, a pyrrolinyl group, animidazolidinyl group, an imidazolinyl group, a pyrazolidinyl group, apyrazolinyl group, a piperidyl group, a piperazinyl group, an indolinylgroup, an isoindolinyl group, a quinuclidinyl group, a morpholinylgroup, and a thioxanthryl group.

Specific examples of the alkylthiocarbonyl group include amethylthiocarbonyl group, a propylthiocarbonyl group, abutylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonylgroup, a decylthiocarbonyl group, an octadecylthiocarbonyl group, and atrifluoromethylthiocarbonyl group.

Specific examples of the arylthiocarbonyl group include a1-naphthylthiocarbonyl group, a 2-naphthylthiocarbonyl group, a4-methylsulfanylphenylthiocarbonyl group, a4-phenylsulfanylphenylthiocarbonyl group, a4-dimethylaminophenylthiocarbonyl group, a4-diethylaminophenylthiocarbonyl group, a 2-chlorophenylthiocarbonylgroup, a 2-methylphenylthiocarbonyl group, a 2-methoxyphenylthiocarbonylgroup, a 2-butoxyphenylthiocarbonyl group, a 3-chlorophenylthiocarbonylgroup, a 3-trifluoromethylphenylthiocarbonyl group, a3-cyanophenylthiocarbonyl group, a 3-nitrophenylthiocarbonyl group, a4-fluorophenylthiocarbonyl group, a 4-cyanophenylthiocarbonyl group, anda 4-methoxyphenylthiocarbonyl group.

In General Formula (OX-1), the monovalent substituent represented by Brepresents an aryl group, a heterocyclic group, an arylcarbonyl group,or a heterocyclic carbonyl group. These groups may have one or moresubstituents, and examples of the substituents include the substituentsdescribed above. In addition, the substituents described above may befurther substituted with other substituents.

Among these, the structures shown below are particularly preferable.

In the following structures, Y, X, and n have the same definitions as Y,X, and n, respectively, in General Formula (OX-2) which will bedescribed later, and the preferred examples thereof are also the same.

In Formula (OX-1), examples of the divalent organic group represented byA include an alkylene group having 1 to 12 carbon atoms, a cycloalkylenegroup, and an alkynylene group, and these groups may have one or moresubstituents. Examples of the substituents include the substituentsdescribed above. Further, the substituents described above may befurther substituted with other substituents.

Among these, as A in Formula (OX-1), from the viewpoints of improvingsensitivity and inhibiting coloring caused by elapse of time duringheating, an unsubstituted alkylene group, an alkylene group substitutedwith an alkyl group (for example, a methyl group, an ethyl group, atert-butyl group, and a dodecyl group), an alkylene group substitutedwith an alkenyl group (for example, a vinyl group and an allyl group),and an alkylene group substituted with an aryl group (for example, aphenyl group, a p-tolyl group, a xylyl group, a cumenyl group, anaphthyl group, an anthryl group, a phenanthryl group, and a styrylgroup) are preferable.

In Formula (OX-1), the aryl group represented by Ar is preferably anaryl group having 6 to 30 carbon atoms, and may have a substituent.Examples of the substituent include the same ones as the substituentsintroduced into the substituted aryl groups, which are exemplified aboveas specific examples of the aryl group which may have a substituent.

Among these, from the viewpoints of improving sensitivity and inhibitingcoloration caused by elapse of time during heating, a substituted orunsubstituted phenyl group is preferable.

In Formula (OX-1), a structure “SAr” formed of Ar and S adjacent theretoin Formula (OX-1) is preferably the following structure from theviewpoint of sensitivity. Incidentally, Me represents a methyl group,and Et represents an ethyl group.

The oxime compound is preferably a compound represented by the followingGeneral Formula (OX-2).

In General Formula (OX-2), R and X each independently represent amonovalent substituent, A and Y each independently represent a divalentorganic group, Ar represents an aryl group, and n represents an integerof 0 to 5. R, A, and Ar in General Formula (OX-2) have the samedefinitions as R, A, and Ar, respectively, in General Formula (OX-1),and the preferred examples thereof are also the same.

Examples of the monovalent substituent represented by X in GeneralFormula (OX-2) include an alkyl group, an aryl group, an alkoxy group,an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonylgroup, an amino group, a heterocyclic group, and a halogen atom. Thesegroups may have one or more substituents, and examples of thesubstituents include the substituents described above. Moreover, thesubstituents described above may be further substituted with othersubstituents.

Among these, from the viewpoints of improving solubility in solvents andabsorption efficiency in a long-wavelength region, X in General Formula(OX-2) is preferably an alkyl group.

Furthermore, n in Formula (2) represents an integer of 0 to 5 andpreferably represents an integer of 0 to 2.

Examples of the divalent organic group represented by Y in GeneralFormula (OX-2) include the following structures. In the followinggroups. “*” represents a position where Y binds to a carbon atomadjacent thereto in Formula (OX-2).

Among these, from the viewpoint of improving sensitivity, the structuresshown below are preferable.

Moreover, the oxime compound is preferably a compound represented by thefollowing General Formula (OX-3) or (OX-4).

In General Formula (OX-3) or (OX-4), R and X each independentlyrepresent a monovalent substituent, A represents a divalent organicgroup, Ar represents an aryl group, and n represents an integer of 0 to5.

R, X, A, Ar, and n in General Formula (OX-3) or (OX-4) have the samedefinitions as R, X, A, Ar, and n, respectively, in General Formula(OX-2), and the preferred examples thereof are also the same.

Specific examples (C-4) to (C-13) of the oxime compound which arepreferably used are shown below, but the present invention is notlimited thereto.

The oxime compound has a maximum absorption wavelength in a wavelengthregion of 350 nm to 500 nm, and preferably has an absorption wavelengthin a wavelength region of 360 nm to 480 nm, and an oxime compoundshowing a high absorbance at 365 nm and 455 nm is particularlypreferable.

From the viewpoint of sensitivity, the molar absorption coefficient at365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000,and more preferably 2,000 to 300,000, and particularly preferably 5,000to 200,000.

The molar absorption coefficient of the compound can be measured using aknown method, but specifically, it is preferable to measure the molarabsorption coefficient by means oft for example, an ultraviolet-visiblespectrophotometer (Carry-5 spectrophotometer manufactured by Varian) byusing an ethyl acetate solvent at a concentration of 0.01 g/L.

In the case where the colored composition of the present inventioncontains a photopolymerization initiator, the content of thephotopolymerization initiator is preferably from 0.1% by mass to 50% bymass, more preferably from 0.5% by mass to 30% by mass, and still morepreferably from 1% by mass to 20% by mass, with respect to the totalsolid contents of the colored composition. Better sensitivity andpattern formability are obtained within the above range.

The composition of the present invention may contain one kind or two ormore kinds of photopolymerization initiator. In the case where thecomposition contains two or more kinds, the total amount thereof ispreferably within the above range.

<Dispersant Resin Agent>

In the case where the colored composition of the present invention has apigment, a dispersant resin agent (pigment dispersant) can be used incombination with other components, as desired.

Examples of the dispersant resin agent which can be used in the presentinvention include polymer dispersants [for example, a polyamide amineand a salt thereof, a polycarboxylic acid and a salt thereof, ahigh-molecular-weight unsaturated acid ester, a modified polyurethane, amodified polyester, a modified poly(meth)acrylate, a (meth)acryliccopolymer, and a naphthalene sulfonate formalin condensate], surfactantssuch as a polyoxyethylene alkyl phosphoric acid ester, a polyoxyethylenealkylamine, and an alkanolamine; and pigment derivatives.

The polymer dispersants can be further classified into straight-chainpolymers, terminal-modified polymers, graft polymers, and blockpolymers, according to the structure.

Examples of the terminal-modified polymers which have a moiety anchoredto the pigment surface include a polymer having a phosphoric acid groupin the terminal as described in JP1991-112992A (JP-H03-112992A),JP2003-533455A, and the like, a polymer having a sulfonic acid group inthe terminal as described in JP2002-273191A, a polymer having a partialskeleton or a heterocycle of an organic dye as described inJP1997-77994A (JP-H09-77994A), and the like. Moreover, a polymerobtained by introducing two or more moieties (acid groups, basic groups,partial skeletons of an organic dye, or heterocycles) anchored to thepigment surface into a polymer terminal as described in JP2007-277514Ais also preferable since this polymer is excellent in dispersionstability.

Examples of the graft polymers having a moiety anchored to the pigmentsurface include polyester-based dispersant and the like, and specificexamples thereof include a product of a reaction between a poly(loweralkyleneimine) and a polyester, which is described in JP1979-37082A(JP-S54-37082A), JP1996-507960A (JP-H08-507960A), JP2009-258668A, andthe like, a product of a reaction between a polyallylamine and apolyester, which is described in JP1997-169821A (JP-H09-169821A) and thelike, a copolymer of a macromonomer and a nitrogen atom monomer, whichis described in JP1998-339949A (JP-H10-339949A), JP2004-37986A,WO2010/110491A, and the like, a graft polymer having a partial skeletonor a heterocycle of an organic dye, which is described inJP2003-238837A, JP2008-9426A, JP2008-81732A, and the like, and acopolymer of a macromonomer and an acid group-containing monomer, whichis described in JP2010-106268A, and the like. From the viewpoint ofdispersibility of a pigment dispersion, dispersion stability, anddevelopability which a colored composition using the pigment exhibits,an amphoteric dispersion resin having basic and acid groups, which isdescribed in JP2009-203462A, is particularly preferable.

As the macromonomer used in production of a graft polymer having amoiety anchored to the pigment surface by radical polymerization, knownmacromonomers can be used. Examples thereof include macromonomers AA-6(polymethyl methacrylate having a methacryloyl group as a terminalgroup), AS-6 (polystyrene having a methacryloyl group as a terminalgroup). AN-6S (a copolymer of styrene and acrylonitrile which has amethacryloyl group as a terminal group), and AB-6 (polybutyl acrylatehaving a methacryloyl group as a terminal group) manufactured byTOAGOSEI, CO., LTD.; Placcel FM5 (a product obtained by adding 5 molarequivalents of ε-caprolactone to 2-hydroxyethyl methacrylate) and FA10L(a product obtained by adding 10 molar equivalents of ε-caprolactone to2-hydroxyethyl acrylate) manufactured by Daicel Corporation; apolyester-based macromonomer described in JP1990-272009A(JP-H02-272009A), and the like. Among these, from the viewpoint ofdispersibility of the pigment dispersion, dispersion stability, and thedevelopability which the colored composition using the pigmentdispersion exhibits, the polyester-based macromonomer excellent inflexibility and solvent compatibility is particularly preferable.Further, a polyester-based macromonomer represented by thepolyester-based macromonomer described in JP1990-272009A(JP-H02-272009A) is most preferable.

As the block polymer having a moiety anchored to the pigment surface,block polymers described in JP2003-49110A, JP2009-52010A, and the likeare preferable.

It is preferable that an oligoimine-based dispersant including anitrogen atom in at least one of the main chain and the side chain isalso used as the pigment dispersant. As the oligoimine-based dispersant,a resin which has a repeating unit having a partial structure X having afunctional group with a pKa of 14 or less, and a side chain including aside chain Y having 40 to 10,000 atoms, and also has a basic nitrogenatom in at least one of the main chain or the side chain, is preferable.

With respect to the oligoimine-based dispersant, reference can be madeto the descriptions in paragraphs “0225” to “0267” of JP2014-063125A,the contents of which are incorporated herein.

The dispersant resin agent which can be used in the present inventioncan be obtained in the form of commercially available products, andspecific examples thereof include “DA-7301” manufactured by KusumotoChemicals, Ltd., “Disperbyk-101 (polyamidamine phosphate), 107(carboxylic acid ester), 110 and 11 (copolymer including an acid group),130 (polyamide), 161, 162, 163, 164, 165, 166, and 170 (polymericcopolymer)”, and “BYK-P104 and P105 (high-molecular-weight unsaturatedpolycarboxylic acid)”, manufactured by BYK-Chemie, “EFKA 4047, 4050,4010, and 4165 (polyurethane-based), EFKA 4330 to 4340 (blockcopolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyesteramide),5765 (high-molecular-weight polycarboxylic acid salt), 6220 (aliphaticpolyester), 6745 (phthalocyanine derivative), and 6750 (azo pigmentderivative)” manufactured by EFKA, “Ajisper PB821, PB822, PB880, andPB881” manufactured by Ajinomoto Fine-Techno Co., Inc., “Flowlen TG-710(urethane oligomer)” and “Polyflow No. 50E, No. 300 (acrylic copolymer)”manufactured by KYOEISHA CHEMICAL Co., LTD., “Disparlon KS-860, 873SN,874, #2150 (aliphatic polyvalent carboxylic acid), #7004 (polyetherester), DA-703-50, DA-705, and DA-725”, manufactured by KusumotoChemicals, Ltd., “Demol RN, N (naphthalene sulfonate formaldehydecondensate), MS, C, SN-B (aromatic sulfonate formaldehyde condensate)”,“Homogenol L-18 (polymeric polycarboxylic acid)”, “Emulgen 920, 930,935, and 985 (polyoxyethylene nonyl phenyl ether)”, and “Acetamine 86(stearylamine acetate)”, manufactured by Kao Corporation, “Solsperse5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240(polyesteramine), 3000, 17000, and 27000 (polymers having a functionalportion in the terminal portion), and 24000, 28000, 32000, and 38500(graft polymers)”, manufactured by The Lubrizol Corporation, “NikkolT106 (polyoxyethylene sorbitan monooleate) and MYS-IEX (polyoxyethylenemonostearate)” manufactured by NIKKO CHEMICALS Co., Ltd., “HinoactT-8000E” and the like manufactured by Kawaken Fine Chemicals Co., Ltd.,“Organosiloxane Polymer KP341” manufactured by Shin-Etsu Chemical Co.,Ltd., “W001: Cationic Surfactant” manufactured by Yusho Co., Ltd.,nonionic surfactants such as polyoxyethylene lauryl ether,polyoxyethylene stearyl ether, polyoxyethylene oleyl ether,polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether,polyethylene glycol dilaurate, polyethylene glycol distearate, andsorbitan aliphatic acid ester, and anionic surfactants such as “W004,W005, and WO17”, “EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKApolymer 400, EFKA polymer 401, and EFKA polymer 450” manufactured byMORISHITA SANGYO Corporation, polymer dispersants such as “Disperse Aid6, Disperse Aid 8. Disperse Aid 15, and Disperse Aid 9100” manufacturedby SAN NOPCO Ltd., “Adeka Pluronic L31, F38, L42, L44, L61, L64, F68,L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, and P-123”manufactured by ADEKA CORPORATION, and “Ionet (product name) S-20”manufactured by Sanyo Chemical Industries, Ltd.

These dispersant resin agents may be used alone or in combination of twoor more kinds thereof. In the present invention, it is particularlypreferable to use a combination of a pigment derivative and a polymerdispersant. Further, the dispersant resin agent may be used incombination with an alkali-soluble resin, together with aterminal-modified polymer having a moiety anchored to the pigmentsurface, a graft polymer, or a block polymer. Examples of thealkali-soluble resin include a (meth)acrylic acid copolymer, an itaconicacid copolymer, a crotonic acid copolymer, a maleic acid copolymer, apartially esterified maleic acid copolymer, and an acidic cellulosederivative having a carboxylic acid in a side chain, and a (meth)acrylicacid copolymer is particularly preferable. In addition, theN-position-substituted maleimide monomers copolymer described inJP1998-300922A (JP-H10-300922A), the ether dimer copolymers described inJP2004-300204A, and the alkali-soluble resins containing a polymerizablegroup described in JP1995-319161A (JP-H07-319161A) are also preferable.

As the dispersant resin agent, the following compound can also be used.

In the case where the colored composition contains a dispersant resinagent, the total content of the dispersant resin agent is preferablyfrom 1 part by mass to 80 parts by mass, more preferably from 5 parts bymass to 70 parts by mass, and still more preferably from 10 parts bymass to 60 parts by mass, with respect to 100 parts by mass of thepigment.

The composition of the present invention may include one kind or two ormore kinds of dispersant resin agent. In the case where the compositionincludes two or more kinds of the dispersant resin agent, the totalamount thereof is preferably within the above range.

Specifically, in the case where a polymer dispersant is used, the amountof the polymer dispersant used is preferably 5 parts by mass to 100parts by mass, and more preferably 10 parts by mass to 80 parts by mass,with respect to 100 parts by mass of the pigment.

Moreover, in the case where a pigment derivative is used in combinationwith other components, the amount of the pigment derivative used ispreferably 1 part by mass to 30 parts by mass, more preferably 1 part bymass to 25 parts by mass, and particularly preferably 1 part by mass to20 pans by mass, with respect to 100 parts by mass of the pigment.

In the colored composition, from the viewpoint of curing sensitivity andcolor density, the total content of the components of the dye and thedispersant is preferably 30% by mass to 90% by mass, more preferably 35%by mass to 80% by mass, and still more preferably 40% by mass to 75% bymass, with respect to the total solid contents constituting the coloredcomposition.

<<Alkali-Soluble Resin>>

It is preferable that the colored composition of the present inventionfurther contains an alkali-soluble resin.

The alkali-soluble resin can be appropriately selected fromalkali-soluble resins which are linear organic high molecular-weightpolymers and have at least one group enhancing alkali-solubility in amolecule (preferably, a molecule having an acrylic copolymer or astyrene-based copolymer as a main chain). From the viewpoint of heatresistance, a polyhydroxystyrene-based resin, a polysiloxane-basedresin, an acrylic resin, an acrylamide-based resin, and anacryl/acrylamide copolymer resin are preferable. Further, from theviewpoint of controlling developability, an acrylic resin, anacrylamide-based resin, and an acryl/acrylamide copolymer resin arepreferable.

Examples of the group promoting alkali-solubility (hereinafter alsoreferred to as an “acid group”) include a carboxyl group, a phosphoricacid group, a sulfonic acid group, a phenolic hydroxyl group, and thelike. The group promoting alkali-solubility is preferably a group whichis soluble in an organic solvent and can be developed by an aqueous weakalkaline solution, and particularly preferred examples thereof include a(meth)acrylic acid. These acid groups may be used alone or incombination of two or more kinds thereof.

Examples of the monomer which can give the acid group afterpolymerization include monomers having a hydroxyl group, such as2-hydroxyethyl (meth)acrylate, monomers having an epoxy group, such asglycidyl (meth)acrylate, and monomers having an isocyanate group, suchas 2-isocyanatoethyl (meth)acrylate. The monomers for introducing theseacid groups may be used alone or in combination of two or more kindsthereof. In order to introduce the acid group into the alkali-solubleresin, for example, the monomer having the acid group and/or the monomerwhich can give the acid group after polymerization (hereinafter referredto as a “monomer for introducing an acid group” in some cases) may bepolymerized as a monomer component.

Incidentally, in the case where a monomer which can give the acid groupafter polymerization is used as a monomer component to introduce theacid group, a treatment for giving the acid group, as will be describedlater, needs to be performed after polymerization.

For production of the alkali-soluble resin, for example, a method usingknown radical polymerization can be applied. Various polymerizationconditions for producing the alkali-soluble resin by radicalpolymerization, such as a temperature, a pressure, the type and amountof a radical initiator, and the type of a solvent, can be easily set bythose skilled in the art, and the conditions can also be determinedexperimentally.

As the linear organic high-molecular weight polymer used as thealkali-soluble resin, polymers having a carboxylic acid in a side chainare preferable, and examples thereof include a methacrylic acidcopolymer, an acrylic acid copolymer, an itaconic acid copolymer, acrotonic acid copolymer, a maleic acid copolymer, a partially esterifiedmaleic acid copolymer, an alkali-soluble phenol resin or the like suchas a novolac resin, an acidic cellulose derivative having a carboxylicacid in a side chain, and a polymer obtained by adding an acid anhydrideto a polymer having a hydroxyl group. In particular, a copolymer of a(meth)acrylic acid and another monomer copolymerizable with the(meth)acrylic acid is suitable as the alkali-soluble resin. Examples ofanother monomer copolymerizable with a (meth)acrylic acid include alkyl(meth)acrylate, aryl (meth)acrylate, and a vinyl compound. Examples ofthe alkyl (meth)acrylate and aryl (meth)acrylate include methyl(meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl(meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl(meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl(meth)acrylate, tolyl (meth)acrylate, naphthyl (meth)acrylate, andcyclohexyl (meth)acrylate. Examples of the vinyl compound includestyrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate,acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfurylmethacrylate, a polystyrene macromonomer, and a polymethyl methacrylatemacromonomer. Examples of the N-position-substituted maleimide monomerdisclosed in JP1998-300922A (JP-H10-300922A) include N-phenylmaleimideand N-cyclohexylmaleimide. Incidentally, other monomers copolymerizablewith a (meth)acrylic acid may be used alone or in combination of two ormore kinds thereof.

It is also preferable that the colored composition contains, as thealkali-soluble resin, a polymer (a) obtained by polymerizing monomercomponents including a compound represented by the following GeneralFormula (ED) and/or a compound represented by the following GeneralFormula (ED2) (each of which may be hereinafter referred to as an “etherdimer” in some cases) as an essential component.

In General Formula (ED), R₁ and R₂ each independently represent ahydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms, whichmay have a substituent.

Thus, the colored composition of the present invention can form a curedcoating film which has extremely excellent heat resistance as well astransparency. In General Formula (ED) which represents the ether dimer,the hydrocarbon group having 1 to 25 carbon atom, represented by R₁ andR₂, which may have a substituent, is not particularly limited, andexamples thereof include linear or branched alkyl groups such as methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, ten-amyl,stearyl, lauryl, and 2-ethylhexyl; aryl groups such as phenyl; alicyclicgroups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl,tricyclodecanyl, isobornyl, adamantyl, and 2-methyl-2-adamantyl; alkylgroups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl;and alkyl groups substituted with an aryl group such as benzyl. Amongthese, from the viewpoints of heat resistance, substituents of primaryor secondary carbon, which are not easily eliminated by an acid or heat,such as methyl, ethyl, cyclohexyl, and benzyl, are preferable.

In General Formula (ED2), R represents a hydrogen atom or an organicgroup having 1 to 30 carbon atoms. With respect to the specific examplesof General Formula (ED2), reference may be made to the description ofJP2010-168539A.

Specific examples of the ether dimer includedimethyl-2,2′-[oxybis(methylene)]bis-2-propenoate,diethyl-2,2′-[oxybis(methylene)]bis-2-propenoate,di(n-propyl)-2,2′-[oxybis(methylene)]bis-2-propenoate,di(isopropyl)-2,2′-[oxybis(methylene)]bis-2-propenoate,di(n-butyl)-2,2′-[oxybis(methylene)]bis-2-propenoate,di(isobutyl)-2,2′-[oxybis(methylene)]bis-2-propenoate,di(tert-butyl)-2,2′-[oxybis(methylene)]bis-2-propenoate,di(tert-amyl)-2,2′-[oxybis(methylene)]bis-2-propenoate,di(stearyl)-2,2′-[oxybis(methylene)]bis-2-propenoate,di(lauryl)-2,2′-[oxybis(methylene)]bis-2-propenoate,di(2-ethylhexyl)-2,2′-[oxybis(methylene)]bis-2-propenoate,di(1-methoxyethyl)-2,2′-[oxybis(methylene)]bis-2-propenoate,di(1-ethoxyethyl)-2,2′-[oxybis(methylene)]bis-2-propenoate,dibenzyl-2,2′-[oxybis(methylene)]bis-2-propenoate,diphenyl-2,2′-[oxybis(methylene)]bis-2-propenoate,dicyclohexyl-2,2′-[oxybis(methylene)]bis-2-propenoate,di(tert-butylcyclohexyl)-2,2′-[oxybis(methylene)]bis-2-propenoate,di(dicyclopentadienyl)-2,2′-[oxybis(methylene)]bis-2-propenoate,di(tricyclodecanyl)-2,2′-[oxybis(methylene)]bis-2-propenoate,di(isobornyl)-2,2′-[oxybis(methylene)]bis-2-propenoate,diadamantyl-2,2′-[oxybis(methylene)]bis-2-propenoate, anddi(2-methyl-2-adamantyl)-2,2′-[oxybis(methylene)]bis-2-propenoate. Amongthese, dimethyl-2,2′-[oxybis(methylene)]bis-2-propenoate,diethyl-2,2′-[oxybis(methylene)]bis-2-propenoate,dicyclohexyl-2,2′-[oxybis(methylene)]bis-2-propenoate, anddibenzyl-2,2′-[oxybis(methylene)]bis-2-propenoate are particularlypreferable. These ether dimers may be used alone or in combination oftwo or more kinds thereof. The structure derived from the compoundrepresented by General Formula (ED) may be copolymerized with othermonomers.

In addition, it is preferable to incorporate an ethylenicallyunsaturated monomer (a) represented by the following Formula (X) as amonomer to be copolymerized with the alkali-soluble resin.

(In Formula (X), R¹ represents a hydrogen atom or a methyl group, R²represents an alkylene group having 2 to 10 carbon atoms, R³ representshydrogen atom or an alkyl group having 1 to 20 carbon atoms, which maycontain a benzene ring. n represents an integer of 1 to 15.)

In Formula (X), the number of carbon atoms of the alkylene group of R²is preferably 2 to 3. Further, the number of carbon atoms of the alkylgroup of R³ is 1 to 20, and more preferably 1 to 10, and the alkyl groupof R³ may contain a benzene ring. Examples of the alkyl group containinga benzene ring, represented by R³, include a benzyl group and a2-phenyl(iso)propyl group.

Examples of the ethylenically unsaturated monomer (a) include ethyleneoxide (EO)-modified (meth)acrylate of phenol. EO- or propylene oxide(PO)-modified (meth)acrylate of paracumylphenol, EO-modified(meth)acrylate of nonylphenol, and PO-modified (meth)acrylate ofnonylphenol. Among these compounds, the EO- or PO-modified(meth)acrylate of paracumylphenol has a higher dispersion effect.

Moreover, in order to improve the crosslinking efficiency of the coloredcomposition in the present invention, an alkali-soluble resin having apolymerizable group may be used. As the alkali-soluble resin having apolymerizable group, an alkali-soluble resins and the like containing anallyl group, a (meth)acryl group, an allyloxyalkyl group, and the likeon a side chain thereof are useful. Examples of the polymer containingthe above polymerizable group include Dianal NR series (manufactured byMitsubishi Rayon Co., Ltd.), Photomer 6173 (a polyurethane acrylicoligomer containing COOH, manufactured by Diamond Shamrock Co., Ltd.),Biscoat R-264 and KS Resist 106 (all manufactured by OSAKA ORGANICCHEMICAL INDUSTRY LTD.), Cyclomer P series and Placcel CF200 series (allmanufactured by DAICEL Corporation), and Ebecryl 3800 (manufactured byDAICEL-UCB Co., Ltd.). As the alkali-soluble resin containing apolymerizable group, a polymerizable double bond-containing acrylicresin modified with urethane, which is a resin obtained by a reaction ofan isocyanate group and an OH group in advance to leave an unreactedisocyanate group and performing a reaction between a compound having a(meth)acryloyl group and an acrylic resin having a carboxyl group, anunsaturated bond-containing acrylic resin which is obtained by areaction between an acrylic resin having a carboxyl group and a compoundhaving both an epoxy group and a polymerizable double bond in amolecule, a polymerizable double bond-containing acrylic resin which isobtained by a reaction between an acid pendant type epoxy acrylateresin, an acrylic resin having an OH group, and a dibasic acid anhydridehaving a polymerizable double bond, a resin obtained by a reactionbetween an acrylic resin having an OH group and a compound havingisocyanate and a polymerizable group, a resin which is obtained bytreating a resin, which has an ester group having an elimination groupsuch as a halogen atom or a sulfonate group in an α-position or aβ-position described in JP2002-229207A and JP2003-335814A on a sidechain, with a base, and the like are preferable.

As the alkali-soluble resin, particularly, a benzyl(meth)acrylate/(meth)acrylic acid copolymer or a multicomponentcopolymer including benzyl (meth)acrylate/(meth)acrylic acid/othermonomers is suitable. Examples thereof also include a benzyl(meth)acrylate/(meth)acrylic acid/2-hydroxyethyl (meth)acrylatecopolymer obtained by copolymerizing 2-hydroxyethyl methacrylate, a2-hydroxypropyl (meth)acrylate/a polystyrene macromonomer/benzylmethacrylate/methacrylic acid copolymer described in JP1995-140654A(JP-H07-140654A), a 2-hydroxy-3-phenoxypropyl acrylate/a polymethylmethacrylate macromonomer/benzyl methacrylate/methacrylic acidcopolymer, a 2-hydroxyethyl methacrylate/a polystyrenemacromonomer/methyl methacrylate/methacrylic acid copolymer, and a2-hydroxyethyl methacrylate/a polystyrene macromonomer/benzylmethacrylate/methacrylic acid copolymer, and particularly preferably, acopolymer of benzyl methacrylate/methacrylic acid.

With respect to the alkali-soluble resin, reference can be made to thedescriptions in paragraphs “0558” to “0571” of JP2012-208494A (“0685” to“0700” of the corresponding to US2012/0235099A), the contents of whichare incorporated herein.

Furthermore, it is preferable to use the copolymers (B) described inparagraph Nos. “0029” to “0063” of JP2012-32767A and the alkali-solubleresins used in Examples of the document; the binder resins described inparagraph Nos. “0088” to “0098” of JP2012-208474A and the binder resinsused in Examples of the document, the binder resins described inparagraph Nos. “0022” to “0032” of JP2012-137531A and the binder resinsin Examples of the document, the binder resins described in paragraphNos. “0132” to “0143” of JP2013-024934A and the binder resins used inExamples of the document, the binder resins described in paragraph Nos.“0092” to “0098” of JP2011-242752A and used in Examples of the document,or the binder resins described in paragraph Nos. “0030” to 0072” ofJP2012-032770A, the contents of which are incorporated herein. MoreSpecifically, the following resins are preferable.

The acid value of the alkali-soluble resin is preferably 30 mgKOH/g to200 mgKOH/g, more preferably 50 mgKOH/g to 150 mgKOH/g, and particularlypreferably 70 mgKOH/g to 120 mgKOH/g.

Furthermore, the weight-average molecular weight (Mw) of thealkali-soluble resin is preferably 2,000 to 50,000, more preferably5,000 to 30,000, and particularly preferably 7,000 to 20,000.

In the case where the colored composition contains an alkali-solubleresin, the content of the alkali-soluble resin is preferably 1% by massto 30% by mass, more preferably 1% by mass to 25% by mass, andparticularly preferably 1% by mass to 20% by mass, with respect to thetotal solid contents of the colored composition.

The colored composition of the present invention may include one kind ortwo or more kinds of alkali-soluble resin. In the case where the coloredcomposition includes two or more kinds of the alkali-soluble resin, thetotal amount thereof is preferably within the range.

<<Crosslinking Agent>>

It is also possible to improve the hardness of the cured film obtainedby curing the colored composition by using a crosslinking agentcomplementarily in the colored composition of the present invention.

The crosslinking agent is not particularly limited as long as it makesit possible to cure a film by a crosslinking reaction, and examplesthereof include (a) an epoxy resin, (b) a melamine compound, a guanaminecompound, a glycoluril compound, or a urea compound substituted with atleast one substituent selected from a methylol group, an alkoxymethylgroup, and an acyloxymethyl group, and (c) a phenol compound, a naphtholcompound, or a hydroxyanthracene compound, which is substituted with atleast one substituent selected from a methylol group, an alkoxymethylgroup, and an acyloxymethyl group. Among these, a polyfunctional epoxyresin is preferable.

With regard to the details of specific examples and the like of thecrosslinking agent, reference can be made to the description ofparagraphs “0134” to “0147” of JP2004-295116A.

In the case where the colored composition of the present inventioncontains a crosslinking agent, the blending amount of the crosslinkingagent is not particularly limited, but is preferably 1% by mass to 30%by mass, and more preferably 1% by mass to 25% by mass, with respect tothe total solid contents of the composition.

The colored composition of the present invention may include one kind ortwo or more kinds of crosslinking agent. In the case where the coloredcomposition includes two or more kinds of the crosslinking agent, thetotal amount thereof is preferably within the range.

<<Polymerization Inhibitor>>

It is preferable to add a small amount of a polymerization inhibitor tothe colored composition of the present invention in order to suppressunnecessary thermal polymerization of the polymerizable compound duringproduction or storage of the colored composition.

Examples of the polymerization inhibitor which can be used in thepresent invention include hydroquinone, p-methoxyphenol,di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone,4,4′-thiobis(3-methyl-6-tert-butylphenol),2,2′-methylenebis(4-methyl-6-tert-butylphenol), and cerium (III)N-nitrosophenyl hydroxylamine.

In the case where the colored composition of the present inventioncontains a polymerization inhibitor, the amount of the polymerizationinhibitor added is preferably about 0.01% by mass to about 5% by masswith respect to the mass of the entire composition.

The composition of the present invention may include one kind or two ormore kinds of polymerization inhibitor. In the case where thecomposition includes two or more kinds of the polymerization inhibitor,the total amount thereof is preferably within the range.

<<Surfactant>>

From the viewpoint of further improving coatability, various surfactantsmay be added to the colored composition of the present invention. As thesurfactants, it is possible to use various surfactants such as afluorine-based surfactant, a nonionic surfactant, a cationic surfactant,an anionic surfactant, and a silicone-based surfactant.

Particularly, if the colored composition of the present inventioncontains a fluorine-based surfactant, liquid characteristics(particularly, fluidity) are further improved when the composition isprepared as a coating liquid, whereby evenness of the coating thicknessor liquid saving properties can be further improved.

That is, in the case where a coating liquid obtained by applying thecolored composition containing a fluorine-based surfactant is used toform a film, the surface tension between a surface to be coated and thecoating liquid is reduced to improve wettability with respect to thesurface to be coated, and enhance coatability with respect to thesurface to be coated. Therefore, even in the case where a thin film ofabout several pm is formed of a small amount of liquid, the coloredcomposition containing a fluorine-based surfactant is effective in thata film with a uniform thickness which exhibits a small extent ofthickness unevenness can be more suitably formed.

The fluorine content in the fluorine-based surfactant is preferably 3%by mass to 40% by mass, more preferably 5% by mass to 30% by mass, andparticularly preferably 7% by mass to 25% by mass. The fluorine-basedsurfactant in which the fluorine content is within the above range iseffective in terms of the evenness of the thickness of the coating filmor liquid saving properties, and the solubility of the surfactant in thecolored composition is also good.

Examples of the fluorine-based surfactant include Megaface F171,Megaface F172, Megaface F173, Megaface F176, Megaface F177, MegafaceF141, Megaface F142, Megaface F143, Megaface F144, Megaface R³⁰,Megaface F437, Megaface F475, Megaface F479, Megaface F482, MegafaceF554, Megaface F780, and Megaface F781 (all manufactured by DICCorporation), Fluorad FC430, FC431, and FC171 (all manufactured bySumitomo 3M), and Surflon S-382. Surflon SC-101, Surtlon SC-103, SurflonSC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383,Surflon 393, and Surflon KH-40 (all manufactured by ASAHI GLASS Co.,Ltd.).

Specific examples of the nonionic surfactant include glycerol,trimethylolpropane, trimethylolethane, and ethoxylate and propoxylatethereof (for example, glycerol propoxylate and glycerin ethoxylate),polyoxyethylene lauryl ether, polyoxyethylene steallyl ether,polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether,polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate,polyethylene glycol distearate, sorbitan fatty acid esters (PluronicL10, L31, L61, L62, 10R5, 17R2, and 25R2, and Tetronic 304, 701, 704,901, 904, and 150R1 manufactured by BASF), and Solseperse 20000(manufactured by The Lubrizol Corporation).

Specific examples of the cationic surfactant include phthalocyaninederivatives (product name: EFKA-745 manufactured by MORISHITA SANGYOCorporation), organosiloxane polymer KP341 (manufactured by Shin-EtsuChemical Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflow No.75, No. 90, and No. 95 (manufactured by KYOEISHA CHEMICAL CO., LTD.),and W001 (manufactured by Yusho Co., Ltd.).

Specific examples of the anionic surfactant include W004, W005, and WO17(manufactured by Yusho Co., Ltd.).

Examples of the silicone-based surfactant include “Toray SiliconeDC3PA”. “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Toray SiliconeSH21PA”, “Toray Silicone SH28PA”, “Toray Silicone SH29PA”, “ToraySilicone SH30PA”, and “Foray Silicone SH8400”, manufactured by DowCorning Toray. “TSF-4440”, “TSF-4300”, “SF-4445”. “TSF-4460”, and“TSF-4452”, manufactured by Momentive Performance Materials Inc.,“KP341”, “KF6001”, and “KF6002”, manufactured by Shin-Etsu Silicones,and “BYK307”, “BYK323”, and “BYK330”, manufactured by BYK-Chemie.

The surfactants may be used alone or in combination of two or more kindsthereof.

In the case where the colored composition of the present inventioncontains a surfactant, the amount of the surfactant added is preferably0.001% by mass to 2.0% by mass and more preferably 0.005% by mass to1.0% by mass, with respect to the total mass of the colored composition.

The composition of the present invention may include one kind or two ormore kinds of surfactant. In the case where the composition includes twoor more kinds of the surfactant, the total amount thereof is preferablywithin the range.

<<Organic Carboxylic Acid and Organic Carboxylic Anhydride>>

The colored composition of the present invention may contain an organiccarboxylic acid having a molecular weight of 1000 or less, and/or anorganic carboxylic anhydride.

Specific examples of the organic carboxylic acid compound include analiphatic carboxylic acid and an aromatic carboxylic acid. Examples ofthe aliphatic carboxylic acid include monocarboxylic acids such asformic acid, acetic acid, propionic acid, butyric acid, valeric acid,pivalic acid, caproic acid, glycolic acid, acrylic acid, and methacrylicacid, dicarboxylic acids such as oxalic acid, malonic acid, succinicacid, glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylicacid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid,maleic acid, and fumaric acid, tricarboxylic acids such astricarballylic acid and aconitic acid, and the like. Examples of thearomatic carboxylic acid include carboxylic acids in which a carboxylgroup is directly bonded to a phenyl group such as a benzoic acid and aphthalic acid, and carboxylic acids in which a phenyl group is bonded toa carboxyl group via a carbon bond. Among these, carboxylic acids havinga molecular weight of 600 or less, particularly those having a molecularweight of 50 to 500, and specifically, maleic acid, malonic acid,succinic acid, and itaconic acid are preferable.

Examples of the organic carboxylic anhydride include aliphaticcarboxylic anhydride and aromatic carboxylic anhydride. Specificexamples thereof include aliphatic carboxylic anhydrides such as aceticanhydride, trichloroacetic anhydride, trifluoroacetic anhydride,tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride,citraconic anhydride, itaconic anhydride, glutaric anhydride,1,2-cyclohexenedicarboxylic anhydride, n-octadecylsuccinic anhydride,and 5-norbornene-2,3-dicarboxylic anhydride. Examples of the aromaticcarboxylic anhydride include phthalic anhydride, trimellitic anhydride,pyromellitic anhydride, and naphthalic anhydride. Among these, thosehaving a molecular weight of 600 or less, particularly having amolecular weight of 50 to 500, specifically, for example, maleicanhydride, succinic anhydride, citraconic anhydride, and itaconicanhydride, are particularly preferable.

In the case where the colored composition of the present inventioncontains an organic carboxylic acid or an organic carboxylic anhydride,the amount of these organic carboxylic acids and/or the organiccarboxylic anhydrizdes added is generally in a range of 0.01% by mass to10% by mass, preferably 0.03% by mass to 5% by mass, and more preferably0.05% by mass to 3% by mass in the total solid contents.

The composition of the present invention may include one kind or two ormore kinds of each of organic carboxylic acids and/or inorganiccarboxylic acids. In the case where the composition includes two or morekinds of the carboxylic acids, the total amount thereof is preferablywithin the above range.

By adding these organic carboxylic acids and/or the organic carboxylicanhydrides having a molecular weight of 1000 or less, it is possible tofurther reduce the amount of the residual undissolved substance of thecolored composition while maintaining high pattern adhesiveness.

If desired, various additives such as a filler, an adhesion promotingagent, an antioxidant, an ultraviolet absorber, and an anti-aggregationagent may be blended into the colored composition. Examples of theseadditives include those described in paragraphs “0155” and “0156” ofJP2004-295116A.

The colored composition of the present invention can contain thesensitizer or the light stabilizer described in paragraph “0078” ofJP2004-295116A, and the thermal polymerization inhibitor described inparagraph “0081” of JP2004-295116A.

The composition of the present invention may include one kind or two ormore kinds of the components. In the case where the composition includestwo or more kinds of the components, the total amount thereof ispreferably within the range.

<Method for Producing Colored Composition>

The colored composition of the present invention is prepared by mixingthe aforementioned components.

Incidentally, when the colored composition is prepared, the respectivecomponents constituting the colored composition may be mixed together atthe same time or mixed together sequentially after being dissolved anddispersed in a solvent. Further, the order of adding the components andthe operation conditions during the mixing are not particularlyrestricted. For example, all the components may be dissolved anddispersed in a solvent at the same time to prepare the composition.Alternatively, if desired, the respective components may beappropriately prepared as two or more solutions and dispersions andmixed at the time of use (at the time of coating) to prepare thecomposition.

The colored composition of the present invention is preferably filteredthrough a filter for the purpose of removing foreign substances,decreasing defectiveness, and the like. As the filter, filters which aretraditionally used for filtration or the like can be used withoutparticular limitation. Examples thereof include filters formed offluororesins such as polytetrafluoroethylene (PTFE), polyamide-basedresins such as nylon-6 and nylon-6,6, and polyolefin resins (includingthose with a high density and an ultrahigh molecular weight) such aspolyethylene and polypropylene (PP). Among these materials,polypropylene (including high-density polypropylene) are preferable.

The pore diameter of the filter is suitably about 0.01 μm to 7.0 μm,preferably 0.01 μm to 3.0 μm, more preferably 0.01 μm to 2.5 μm, stillmore preferably 0.01 μm to 2.0 μm, and particularly preferably 0.05 μmto 0.5 μm. Within the above range, it becomes possible to remove minuteforeign substances which hinder the preparation of a uniform and smoothcolored radiation-sensitive composition layer.

When using the filter, different filters may be used in combination. Atthis time, the filtering in the first filtration may be carried out onlyonce or twice or more times in the first filter.

In addition, filters having different pore diameters within theaforementioned range may be combined with each other. Here, with respectto the pore diameter, reference can be made to values officiallymeasured by a filter maker. As a commercially available filter, thefilter can be selected from various filters supplied from PallCorporation Japan. ADVANTEC Co., Ltd., Japan Entegris, Inc. (formerlyJapan Microlis), KITZ MICRO FILTER CORPORATION, or the like.

As a second filter, a filter formed of the same material or the like asthat of the aforementioned first filter can be used.

For example, the filtering in the first filtration is carried out onlyfor a dispersion, and the second filtering may be carried out.

The colored composition of the present invention is preferably used forforming a colored layer of a color filter. More specifically, since thecolored composition of the present invention can form a cured filmhaving excellent heat resistance and color characteristics, the coloredcomposition of the present invention is suitably used for forming acolored pattern (colored layer) of a color filter. Further, the coloredcomposition of the present invention can be suitably used for forming acolored pattern of a color filter or the like used in a solid-stateimaging element (for example, a CCD and a CMOS) or an image displaydevice such as a liquid crystal display (LCD). Further, the compositioncan also be suitably used in an application of the manufacture of aprint ink, an ink jet ink, a coating material, or the like. Among these,the composition can be suitably used in an application of themanufacture of a color filter for a solid-state imaging element such asa CCD and a CMOS.

The present invention also relates to a polymer having the repeatingunit(s) represented by General Formula (A4-1) and/or (A4-3). Further,the present invention also relates to a xanthene dye represented byGeneral Formula (A5).

<Cured Film, Pattern Forming Method, Color Filter, and Method forProducing Color Filter>

Next, the cured film, the pattern forming method, and the color filterin the present invention will be described in detail with reference toproduction methods thereof.

The cured film of the present invention is formed by curing the coloredcomposition of the present invention. Such a cured film is preferablyused in a color filter.

In the pattern forming method of the present invention, a coloredcomposition layer is formed on a support using the colored compositionof the present invention, and undesired areas are removed to form acolored pattern.

The pattern forming method of the present invention can be suitablyapplied for forming a colored pattern (pixel) which a color filter has.

With the composition of the present invention, a color filter may bemanufactured by forming a pattern by so-called photolithography, or apattern can be formed by a dry etching method.

That is, as a first method for manufacturing a color filter, a methodfor manufacturing a color filter, including, applying the coloredcomposition of the present invention onto a support to form a coloredcomposition layer, a step of patternwise exposing the coloredcomposition layer, and a step of removing an unexposed area bydevelopment to form a colored pattern, is exemplified.

Furthermore as a second method for manufacturing a color filter, amethod for manufacturing a color filter, including, a step of applyingthe colored composition of the present invention onto a support to forma colored composition layer and curing the colored composition layer toform a colored layer, a step of forming a photoresist layer on thecolored layer, a step of patterning the photoresist layer by exposureand development to obtain a resist pattern, and a step of dry-etchingthe colored layer using the resist pattern as an etching mask to form acolored pattern.

In the present invention, it is more preferable that the color filter ismanufactured by photolithography.

Details thereof will be described below.

Hereinafter, the respective steps in the pattern forming method of thepresent invention will be described will be described in detail withrespect to the method for manufacturing a color filter for a solid-stateimaging element, but the present invention is not limited to the method.Hereinafter, the color filter for a solid-state imaging element may besimply referred to as a “color filter” in some cases.

<Step of Forming Colored Composition Layer>

In the step of forming a colored composition layer, the coloredcomposition of the present invention is applied onto a support to form acolored composition layer.

As the support which can be used in the present step, for example, asubstrate for a solid-state imaging element, which is formed byproviding an imaging element (light-receiving element) such as a chargecoupled device (CCD) or a complementary metal-oxide semiconductor (CMOS)onto a substrate (for example, a silicon substrate) can be used.

The colored pattern in the present invention may be formed on thesurface (front surface) on which an imaging element is formed or on thesurface (back surface) where an imaging element is not formed, of asubstrate for a solid-state imaging element.

A light shielding film may be disposed between the colored patterns in asolid-state imaging element or on the back surface of the substrate fora solid-state imaging element.

In addition, if desired, an undercoat layer may be disposed onto thesupport in order to improve adhesiveness between the support and theupper layer, prevent diffusion of substances, or planarize the substratesurface. A solvent, an alkali-soluble resin, a polymerizable compound, apolymerization inhibitor, a surfactant, a photopolymerization initiator,or the like can be blended into the undercoat layer, and it ispreferable that these respective components are appropriately selectedfrom the components blended into the composition of the presentinvention.

As the method for applying the colored composition of the presentinvention onto the support, various coating methods such as slitcoating, ink jet coating, spin coating, cast coating, roll coating, andscreen printing can be applied.

Drying (pre-baking) of the colored composition layer applied onto thesupport can be carried out in a hot plate, an oven, or the like at atemperature of 50° C. to 140° C. for 10 seconds to 300 seconds.

<<Case of Forming Pattern by Photolithography>>

<<<Exposing Step>>>

In the exposing step, the colored composition layer formed in thecolored composition layer forming step is patternwise exposed through amask having a predetermined mask pattern by using, for example, anexposure device such as a stepper. Thus, a cured film is obtained.

As radiation (light) usable in exposure, particularly, ultraviolet rayssuch as a g-ray and an i-ray are preferably used (particularly, an i-rayis preferably used). The irradiation dose (exposure dose) is preferably30 mJ/cm² to 1500 mJ/cm², more preferably 50 mJ/cm² to 1000 mJ/cm², andmost preferably 80 mJ/cm² to 500 mJ/cm².

The film thickness of the cured film (colored film) is preferably 1.0 μmor less, more preferably 0.1 μm to 0.9 μm, and still more preferably 0.2μm to 0.8 μm.

It is preferable to set the film thickness to 1.0 μm or less since highresolution and high adhesiveness are obtained.

Moreover, in this step, a cured film having a small film thickness of0.7 μm or less can be suitably formed. Further, if the obtained curedfilm is subjected to a development treatment in a pattern forming stepwhich will be described later, it is possible to obtain a coloredpattern which is a thin film and exhibits excellent developability andreduced surface roughness with an excellent pattern shape.

<<Developing Step>>>

Thereafter, by performing an alkaline developing treatment, the coloredcomposition layer in an area not irradiated with light in the exposingstep is eluted into an aqueous alkaline solution, and as a result, onlya photocured area remains.

As a developing liquid, an organic alkaline developing liquid notdamaging an imaging element, a circuit, or the like in an underlayer ispreferable. The development temperature is usually 20° C. to 30° C., andthe development time is 20 seconds to 90 seconds in the related art. Inorder to further remove residues, development is recently carried outfor 120 seconds to 180 seconds in some cases. Further, in order toimprove residue removal properties, a step of sufficiently shaking thedeveloping liquid every 60 seconds and newly supplying a developingliquid is repeated plural times in some cases.

Examples of an alkaline agent used for the developing liquid includeorganic alkaline compounds such as aqueous ammonia, ethylamine,diethylamine, dimethyl ethanolamine, tetramethyl ammonium hydroxide,tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide,tetrabutyl ammonium hydroxide, benzyltrimethyl ammonium hydroxide,choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene.An aqueous alkaline solution obtained by diluting these alkaline agentswith pure water so as to yield a concentration of the alkaline agent of0.001% by mass to 10% by mass, and preferably 0.01% by mass to 1% bymass is preferably used as the developing liquid.

Incidentally, inorganic alkali may be used for the developing liquid,and as the inorganic alkali, for example, sodium hydroxide, potassiumhydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate,sodium metasilicate, and the like are preferable.

Furthermore, in the case where a developing liquid formed of such anaqueous alkaline solution is used, the pattern is generally cleaned(rinsed) with pure water after development.

Next, it is preferable to carry out a heating treatment (post-baking)after drying. If a multi-colored pattern is formed, the above steps canbe sequentially repeated for each color to produce a cured film. Thus, acolor filter is obtained.

The post-baking is a heating treatment performed after development so asto complete curing, and in the post-baking, a thermal curing treatmentis carried out usually at 100° C. to 240° C., and preferably at 200° C.to 240° C.

The post-baking treatment can be carried out on the coating filmobtained after development in a continuous or batch manner, by usingheating means such as a hot plate, a convection oven (a hot-aircirculation type drier), and a high-frequency heater under theconditions described above.

<Case of Forming Pattern by Dry Etching Method>

In the case of forming a pattern by a dry etching method, the methodpreferably includes a step of applying the colored composition of thepresent invention onto a support to form a colored composition layer andcuring the colored composition layer to form a colored layer, a step offorming a photoresist layer on the colored layer, a step of patterningthe photoresist layer by exposure and development to obtain a resistpattern, and a step of dry-etching the colored layer using the resistpattern as an etching mask.

For the colored layer, the dry etching can be carried out with anetching gas, using a patterned photoresist layer as a mask.Specifically, a positive-type or negative-type radiation-sensitivecomposition is applied onto the colored layer and dried to form aphotoresist layer. In the formation of the photoresist layer, it ispreferable to further carry out a pre-baking treatment. In particular,as a process for forming a photoresist, a configuration in which apost-exposure heating treatment (PEB) or a post-development heatingtreatment (post-baking treatment) is carried out is preferable.

As the photoresist, for example, a positive-type radiation-sensitivecomposition is used. As the positive-type radiation-sensitivecomposition, a positive-type resist composition suitable for apositive-type photoresist, which responds to radiation, for example, anultraviolet ray (a g-ray, an h-ray, or an i-ray), a far ultraviolet rayincluding an excimer laser and the like, an electron beam, an ion beam,or an X-ray, can be used. Among the radiations, a g-ray, an h-ray, or ani-ray is preferable, among which the i-ray is more preferable.

Specifically, as the positive-type radiation-sensitive composition, acomposition containing a quinonediazide compound and an alkali-solubleresin is preferable. The positive-type radiation-sensitive compositioncontaining a quinonediazide compound and an alkali-soluble resinutilizes a quinonediazide group being decomposed to generate a carboxylgroup by light irradiation at a wavelength of 500 nm or less, and as aresult, the quinonediazide compound is shifted from an alkali-insolublestate to an alkali-soluble state. Since this positive-type photoresistis remarkably excellent in the resolving power, it is used for themanufacture of an integrated circuit, for example, IC and LSI. Examplesof the quinonediazide compound include a naphthoquinonediazide compound.Examples of commercially available products thereof include “FHi622BC”(manufactured by FUJIFILM Electronics Materials Co., Ltd.).

The thickness of the photoresist layer is preferably 0.1 μm to 3 μm,more preferably 0.2 μm to 2.5 μm, and still more preferably 0.3 μm to 2μm. Incidentally, coating of the photoresist layer can be suitablycarried out using the coating method described with respect to theabove-described colored layer.

Next, a resist pattern (patterned photoresist layer) in which a resistthrough-hole group is disposed is formed by exposing and developing thephotoresist layer. The formation of the resist pattern can be carriedout by appropriately optimizing heretofore known techniques ofphotolithography without particular limitation. By providing the resistthrough-hole group in the photoresist layer by exposure and development,the resist pattern which is used as an etching mask in the subsequentetching is provided on the colored layer.

Exposure of the photoresist layer can be carried out by exposing apositive-type or negative-type radiation-sensitive composition to ag-ray, an h-ray, or an i-ray, and preferably to an i-ray through apredetermined mask pattern. After the exposure, a development treatmentis carried out using a developing liquid to remove the photoresistcorresponding to the region where a colored pattern is to be formed.

As the developing liquid, any developing liquid which does not affect acolored layer containing a coloring agent and dissolves the exposed areaof a positive resist or the uncured area of a negative resist may beused, and for example, a combination of various organic solvents or anaqueous alkaline solution is used. As the aqueous alkaline solution, anaqueous alkaline solution prepared by dissolving an alkaline compound toyield a concentration of 0.001% by mass to 10% by mass, and preferably0.01% by mass to 5% by mass is suitable. Examples of the alkalinecompound include sodium hydroxide, potassium hydroxide, sodiumcarbonate, sodium silicate, sodium metasilicate, aqueous ammonia,ethylamine, diethylamine, dimethylemanolamine, tetramethylammoniumhydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine,and 1,8-diazabicyclo-[5.4.0]-7-undecene. Incidentally, in the case wherean aqueous alkaline solution is used as the developing liquid, acleaning treatment with water is generally carried out afterdevelopment.

Next, the colored layer is patterned by dry etching so as to form athrough-hole group in the colored layer using the resist pattern as anetching mask. Thus, a colored pattern is formed. The through-hole groupis provided checkerwise in the colored layer. Thus, a first coloredpattern having the through-hole group provided in the colored layer hasa plurality of first quadrangular colored pixels checkerwise.

Specifically, in the dry etching, the colored layer is dry-etched usinga resist pattern as an etching mask. Representative examples of the dryetching include the methods described in the respective gazettes ofJP1984-126506A (JP-S59-126506A). JP1984-46628A (JP-S59-46628A).JP1983-9108A (JP-S58-9108A), JP1983-2809A (JP-S58-2809A), JP1982-148706A(JP-S57-148706A), JP1986-41102A (JP-S61-41102A), and the like.

It is preferable that the dry etching is carried out in a configurationas described below from the viewpoint of forming a pattern cross-sectioncloser to that of a rectangle or of further reducing damage to asupport.

A configuration is preferable, which includes a first-stage etching ofetching up to an area (depth) where the support is not revealed by usinga mixed gas of a fluorine-based gas and an oxygen gas (O₂), asecond-stage etching of preferably etching up to the vicinity of an area(depth) where the support is revealed by using a mixed gas of a nitrogengas (N₂) and an oxygen gas (O₂) after the first-stage etching, and anover-etching carried out after the support has been revealed. A specificmanner of the dry etching as well as the first-stage etching, thesecond-stage etching, and the over-etching will be described below.

The dry etching is carried out by determining the etching conditions inadvance in the following manner.

(1) An etching rate (nm/min) in the first-stage etching and an etchingrate (nm/min) in the second-stage etching are calculated, respectively.(2) A time for etching a predetermined thickness in the first-stageetching and a time for etching a predetermined thickness in thesecond-stage etching are calculated, respectively. (3) The first-stageetching is carried out according to the etching time calculated in (2)above. (4) The second-stage etching is carried out according to theetching time calculated in (2) above. Alternatively, an etching time isdetermined by endpoint detection, and the second-stage etching may becarried out according to the determined etching time. (5) Theover-etching time is calculated in response to the total time of (3) and(4) above, and the over-etching is carried out.

The mixed gas used in the first-stage etching step preferably contains afluorine-based gas and an oxygen gas (O₂) from the viewpoint ofprocessing an organic material of the film to be etched into a rectangleshape. The first-stage etching step may avoid damage to the support byadopting the configuration of etching up to an area where the support isnot revealed. After the etching is carried out up to an area where thesupport is not revealed by the mixed gas of a fluorine-based gas and anoxygen gas in the first-stage etching step, etching treatment in thesecond-stage etching step and etching treatment in the over-etching stepare preferably carried out by using the mixed gas of a nitrogen gas andan oxygen gas from the viewpoint of avoiding damage to the support.

It is important that a ratio between the etching amount in thefirst-stage etching step and the etching amount in the second-stageetching step is determined so as not to deteriorate the linearity by theetching treatment in the first-stage etching step. Incidentally, theratio of the etching amount in the second-stage etching step in thetotal etching amount (the sum of the etching amount in the first-stageetching step and the etching amount in the second-stage etching step) ispreferably in a range of more than 0% and 50% or less, and morepreferably 10% to 20%. The etching amount means an amount determined bya difference between the remaining film thickness of the etched film andthe film thickness of the film before the etching.

Furthermore, the etching preferably includes an over-etching treatment.The over-etching treatment is preferably carried out by determining anover-etching rate. The over-etching rate is preferably calculated froman etching treatment time which is carried out at first. Although theover-etching rate may be arbitrarily determined, it is preferably 30% orless, more preferably 5% to 25%, and particularly preferably 10% to 15%,of the etching processing time in the etching steps, from the viewpointof etching resistance of the photoresist and preservation of thelinearity of the etched pattern.

Next, the resist pattern (that is, the etching mask) remaining after theetching is removed. The removal of the resist pattern preferablyincludes a step of supplying a peeling solution or a solvent on theresist pattern to make the resist pattern be in a removable state, and astep of removing the resist pattern using cleaning water.

The step of supplying a peeling solution or a solvent on the resistpattern to make the resist pattern be in a removable state includes, forexample, a step of paddle development by supplying a peeling solution ora solvent at least on the resist pattern and retaining for apredetermined time. The time for retaining the peeling solution or asolvent is not particularly limited, and is preferably several tens ofseconds to several minutes.

Moreover, the step of removing the resist pattern using cleaning waterincludes, for example, a step of removing the resist pattern by sprayingcleaning water from a spray-type or shower-type spray nozzles onto theresist pattern. As the cleaning water, pure water is preferably used.The spray nozzles include spray nozzles having a spray area which coversthe entire support and mobile spray nozzles having a mobile area whichcovers the entire support. In the case where the spray nozzles aremobile spray nozzles, the resist pattern can be more effectively removedby moving the mobile spray nozzles twice or more from the center ofsupport to the edge of the support to spray cleaning water in the stepof removing the resist pattern.

The peeling solution generally contains an organic solvent and mayfurther contain an inorganic solvent. Examples of the organic solventinclude 1) a hydrocarbon-based compound, 2) a halogenatedhydrocarbon-based compound, 3) an alcohol-based compound, 4) an ether-or acetal-based compound, 5) a ketone- or aldehyde-based compound, 6) anester-based compound, 7) a polyhydric alcohol-based compound, 8) acarboxylic acid- or its acid anhydride-based compound, 9) a phenol-basedcompound, 10) a nitrogen-containing compound, 11) a sulfur-containingcompound, and 12) a fluorine-containing compound. The peeling solutionpreferably contains a nitrogen-containing compound, and more preferablycontains an acyclic nitrogen-containing compound and a cyclicnitrogen-containing compound.

The acyclic nitrogen-containing compound is preferably an acyclicnitrogen-containing compound having a hydroxyl group. Specific examplesthereof include monoisopropanolamine, diisopropanolamine,triisopropanolamine, N-ethylethanolamine, N,N-dibutylethanolamine,N-butylethanolamine, monoethanolamine, diethanolamine, andtriethanolamine, among which monoethanolamine, diethanolamine, andtriethanolamine are preferable, and monoethanolamine (H₂NCH₂CH₂OH) ismore preferable. Further, examples of the cyclic nitrogen-containingcompound include isoquinoline, imidazole, N-ethylmorpholine,ε-caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, α-picoline,β-picoline, γ-picoline, 2-pipecoline, 3-pipecoline, 4-pipecoline,piperazine, piperidine, pyrazine, pyridine, pyrrolidine,N-methyl-2-pyrrolidone. N-phenyl morpholine, 2,4-lutidine, and2,6-lutidine, among which N-methyl-2-pyrrolidone and N-ethyl morpholineare preferable, and N-methyl-2-pyrrolidone (NMP) is more preferable.

The peeling solution preferably includes both the acyclicnitrogen-containing compound and the cyclic nitrogen-containingcompound, more preferably contains at least one selected frommonoethanolamine, diethanolamine, and triethanolamine as the acyclicnitrogen-containing compound, and at least one selected fromN-methyl-2-pyrrolidone and N-ethyl morpholine as the cyclicnitrogen-containing compound, and still more preferably containsmonoethanolamine and N-methyl-2-pyrrolidone.

In the removal with the peeling solution, it is sufficient that theresist pattern formed on the first colored pattern is removed, and inthe case where a deposit of an etching product is attached to the sidewall of the first colored pattern, it is not always necessary tocompletely remove the deposit. The deposit means an etching productattached and deposited to the side wall of colored layer.

For the peeling solution, it is preferable that the content of theacyclic nitrogen-containing compound is 9 parts by mass to 11 parts bymass with respect to 100 parts by mass of the peeling solution, and thecontent of the cyclic nitrogen-containing compound is 65 parts by massto 70 parts by mass with respect to 100 parts by mass of the peelingsolution. The peeling solution is preferably one prepared by diluting amixture of the acyclic nitrogen-containing compound and the cyclicnitrogen-containing compound with pure water.

Incidentally, the method for manufacturing a color filter of the presentinvention may have a step known as a method for manufacturing a colorfilter for a solid-state imaging element, if desired, as a step otherthan the above steps. For example, the method may include a curing stepof curing the formed colored pattern by heating and/or exposure, ifdesired, after the colored composition layer forming step, the exposingstep, and the pattern forming step are carried out.

Moreover, in the case of using the colored composition of the presentinvention, there are some cases where the contamination caused when anozzle of an ejection portion or a piping portion of a coating device isclogged, or the colored composition or a pigment adheres to or isprecipitated or dried inside the coating machine may occur. Thus, inorder to efficiently clean off the contamination caused by the coloredcomposition of the present invention, it is preferable to use thesolvent relating to the present configuration as described above as acleaning liquid. In addition, the cleaning liquids described inJP1995-128867A (JP-H07-128867A). JP1995-146562A (JP-H07-146562A),JP1996-278637A (JP-H08-278637A), JP2000-273370A, JP2006-85140A,JP2006-291191A, JP2007-2101A, JP2007-2102A, JP2007-281523A, and the likecan also be suitably used as a liquid for removing the coloredcomposition according to the present invention by cleaning.

Among the above, alkylene glycol monoalkyl ether carboxylate andalkylene glycol monoalkyl ether are preferable.

These solvents may be used alone or as a mixture of two or more kindsthereof. In the case where two or more kinds thereof are mixed, it ispreferable to mix a solvent having a hydroxyl group with a solvent nothaving a hydroxyl group. The mass ratio between the solvent having ahydroxyl group and the solvent not having a hydroxyl group is 1/99 to99/1, preferably 10/90 to 90/10, and still more preferably 20/80 to80/20. A mixed solvent in which propylene glycol monomethyl etheracetate (PGMEA) is mixed with propylene glycol monomethyl ether (PGME)at a ratio of 60/40 is particularly preferable. Incidentally, in orderto improve the permeability of the cleaning liquid with respect to thecontaminant, the aforementioned surfactants relating to the presentcomposition may be added to the cleaning liquid.

Since the color filter of the present invention uses the coloredcomposition of the present invention, exposure having an excellentexposure margin can be carried out, and the formed colored pattern(colored pixel) has an excellent pattern shape. Further, since thesurface roughness of the pattern and the amount of residues in adeveloped area are inhibited, excellent color characteristics areexhibited.

The color filter of the present invention can be suitably used for asolid-state imaging element such as a CCD and a CMOS, and is suitablypreferable for a CCD, a CMOS, and the like with a high resolution,having more than 1,000,000 pixels. The color filter for a solid-stateimaging element of the present invention can be used as, for example, acolor filter disposed between a light-receiving portion of each pixelconstituting a CCD or a CMOS and a microlens for condensing light.

Incidentally, the film thickness of the colored pattern (colored pixel)in the color filter of the present invention is preferably 2.0 μm orless, more preferably 1.0 μm or less, and still more preferably 0.7 μmor less.

Moreover, the size (pattern width) of the colored pattern (coloredpixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, andparticularly preferably 1.7 μm or less.

<Solid-State Imaging Element>

The solid-state imaging element of the present invention includes thecolor filter of the present invention. The constitution of thesolid-state imaging element of the present invention is not particularlylimited as long as the solid-state imaging element is constituted toinclude the color filter in the present invention and functions as asolid-state imaging element. However, for example, the solid-stateimaging element can be constituted as below.

That is, the constitution is as follows: a plurality of photodiodesforming a light-receiving area of a solid-state imaging element (a CCDimage sensor, a CMOS image sensor, or the like) and a transmissionelectrode formed of polysilicon or the like are provided on a support; alight-shielding film which is made of, for example, tungsten and hasopenings corresponding to only light-receiving portions of thephotodiodes is provided on the photodiodes and the transmissionelectrode; a device protecting film which is made of, for example,silicon nitride is formed on the light-shielding film so as to cover theentire surface of the light-shielding film and the light-receivingportions of the photodiodes; and the color filter for a solid-stateimaging element according to the present invention is provided on thedevice protecting film.

In addition, the solid-state imaging element may also be configured, forexample, such that it has a light-collecting unit (for example, amicrolens or the like, which shall apply hereinafter) provided on thedevice protecting film and under a color filter (on the side closer to asupport) or has a light-collecting unit on a color filter.

<Image Display Device>

The color filter of the present invention can be used not only for asolid-state imaging element, but also for an image display device suchas a liquid crystal display device and an organic EL display device. Inparticular, the color filter is suitable for the applications of aliquid crystal display device. The liquid crystal display deviceincluding the color filter of the present invention can display ahigh-quality image showing a good tone of the display image and havingexcellent display characteristics.

The definition of display devices or details of the respective displaydevices are described in, for example, “Electronic Display Device (AkioSasaki, Kogyo Chosakai Publishing Co., Ltd., published in 1990)”,“Display Device (Toshiyuki Ibuki, Sangyo Publishing Co., Ltd., publishedin 1989), and the like. In addition, the liquid crystal display deviceis described in, for example, “Liquid Crystal Display Technology forNext Generation (edited by Tatsuo Uchida, Kogyo Chosakai Publishing Co.,Ltd., published in 1994)”. The liquid crystal display device to whichthe present invention can be applied is not particularly limited, andfor example, the present invention can be applied to liquid crystaldisplay devices employing various systems described in the “LiquidCrystal Display Technology for Next Generation”.

The color filter of the present invention may be used for a liquidcrystal display device using a color TFT system. The liquid crystaldisplay device using a color TFT system is described in, for example,“Color TFT Liquid Crystal Display (KYORITSU SHUPPAN Co., Ltd., publishedin 1996)”. Further, the present invention can be applied to a liquidcrystal display device having an enlarged view angle, which uses anin-plane switching driving system such as IPS and a pixel divisionsystem such as MVA, or to STN, TN, VA, OCS, FFS, R-OCB, and the like.

In addition, the color filter in the present invention can be providedto a Color-filter On Array (COA) system which is a bright andhigh-definition system. In the liquid crystal display device of the COAsystem, the characteristics required for a color filter layer need toinclude characteristics required for an interlayer insulating film, thatis, a low dielectric constant and resistance to a peeling solution insome cases, in addition to the generally required characteristics asdescribed above. In the color filter of the present invention, a dyemultimer having an excellent hue is used. Accordingly, the color purity,light-transmitting properties, and the like are good, and the tone ofthe colored pattern (pixel) is excellent. Consequently a liquid crystaldisplay device of a COA system which has a high resolution and isexcellent in long-term durability can be provided. Incidentally, inorder to satisfy the characteristics required for a low dielectricconstant, a resin coat may be provided on the color filter layer.

These image display systems are described in, for example, p. 43 of “EL,PDP, and LCD Display Technologies and Recent Trend in Market (TORAYRESEARCH CENTER, Research Department, published in 2001)”, and the like.

Furthermore, in the present invention, the color filter can also bepreferably used for display in a micro-OLED system. These image displaysystems are described in, for example, p. 43 of “EL, PDP, and LCDDisplay Technologies and Recent Trend in Market (TORAY RESEARCH CENTER,Research Department, published in 2001)”, and the like.

The liquid crystal display device including the color filter in thepresent invention is constituted with various members such as anelectrode substrate, a polarizing film, a phase difference film, abacklight, a spacer, and a view angle compensation film, in addition tothe color filter of the present invention. The color filter of thepresent invention can be applied to a liquid crystal display deviceconstituted with these known members. These members are described in,for example, “'94 Market of Peripheral Materials And Chemicals of LiquidCrystal Display (Kentaro Shima, CMC Publishing Co., Ltd., published in1994)” and “2003 Current Situation of Market Relating to Liquid Crystaland Prospects (Vol. 2) (Ryokichi Omote, Fuji Chimera Research Institute.Inc., published in 2003)”.

The backlight is described in SID Meeting Digest 1380 (2005) (A. Konno,et al.), December Issue of Monthly “Display”, 2005, pp. 18-24 (YasuhiroShima) and pp. 25-30 (Takaaki Yagi) of the literature, and the like.

If the color filter in the present invention is used in a liquid crystaldisplay device, high contrast can be realized when the color filter iscombined with a three-wavelength tube of a cold cathode tube known inthe related art. Further, if a light source of LED in red, green, andblue (RGB-LED) is used as a backlight, a liquid crystal display devicehaving high luminance, high color purity, and good color reproducibilitycan be provided.

EXAMPLES

Hereinafter, the present invention will be described in more detail withreference to Examples, but is not limited to the Examples below as longas there is no deviation from the gist of the present invention.Incidentally, “%” and “part(s)” are based on mass unless otherwisespecified.

Synthesis Examples of Dye Compound A-1

<Synthesis of Intermediate 1>

50 parts of DCSF (manufactured by Chugai Kasei Co Ltd.), 74.76 parts of2,6-dimethylaniline, 27.58 parts of zinc chloride, and 200 parts ofsulfolane were put into a flask and the mixture was stirred at anexternal temperature of 200° C. for 4 hours. Thereafter, the obtainedreaction solution was left to be cooled to room temperature and addeddropwise to 500 parts of 2 N hydrochloric acid, and the precipitatedcrystal was separated by filtration. The crystal was dispersed andwashed with 300 parts of acetonitrile at 40° C., collected byfiltration, and air-dried for 10 hours to obtain 46.5 parts (yield:65.6%) of an intermediate 1.

<Synthesis of Intermediate 2>

20 parts of the intermediate 1 and 106 parts of phosphorus oxychloridewere put into a flask and the mixture was stirred at 60° C. for 2 hours.The obtained reaction solution was left to be cooled to roomtemperature, the reaction solution was added dropwise to 1500 parts ofice water, and the mixture was stirred for 30 minutes. The obtainedcrystal was separated by filtration, washed with 200 parts of water, andair-dried for 10 hours to obtain 18.5 parts (yield: 89.4%) of anintermediate 2.

<Synthesis of Dye Compound A-1>

7 parts of the intermediate 2 and 1.94 parts oftrifluoromethylsulfonamide were dissolved in 40 parts of chloroform,1.55 parts of triethylamine was added dropwise, and the mixture wasstirred at room temperature for 1 hour. Thereafter, 100 parts of waterwas added to the obtained reaction solution to perform water-washing andthen the organic layer was collected by separation. The organic layerwas dried over sodium sulfate, purified by column chromatography, andconcentrated under reduced pressure to obtain a dye compound A-1 (3parts (yield: 36%)).

The dye compound A-1 was subjected to ¹H NMR spectrum measurement. Themeasurement was carried out using 400 MHz and dimethyl sulfoxide (DMSO).Product name: AV-400, manufactured by Bruker Co. Ltd., was used as ameasurement device.

δ 2.15-2.25 (12H, m), 5.95-6.31 (4H, m), 6.95-7.4 (8H, m), 7.4-7.53 (1H,m), 7.7-7.9 (2H, m), 8.11-8.25 (1H, m), 9.93-10.12 (2H, m).

<Synthesis of Dye Compound A-2>

A dye compound A-2 was synthesized in the same manner as in the methodfor synthesizing the dye compound A-1 except thattrifluoromethylsulfonamide was changed to the same moles ofbistrifluoromethylsulfonylmethane in the method for synthesizing the dyecompound A-1.

<Synthesis of Intermediate 3>

50 parts of p-acetoxystyrene, 150 parts of ethyl acetate, and 89.2 partsof a 28% methanol solution of sodium methoxide were put into a flask,and the mixture was stirred at room temperature for 1 hour. To theobtained reaction solution was added 500 parts of a 1 N hydrochloricacid solution, and then the ethyl acetate layer was collected byseparation. The ethyl acetate layer was washed and the ethyl acetatelayer after washing was dried over magnesium sulfate. 4.63 parts oftriethylamine was added to the solution after drying and the mixture wascooled to 0° C. 13.8 parts of1,3-bis(fluorosulfonyl)-1,1,2,2,3,3-hexafluorobutane (EF-3000manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.) wasadded dropwise thereto under cooling and the mixture was stirred for 30minutes. Thereafter, 500 parts of aqueous ammonia was added thereto andthe mixture was stirred for 30 minutes. The reaction solution wasneutralized with a 1 N hydrochloric acid solution, then washed with 500parts of saturated physiologicalsaline, dried over magnesium sulfate,and concentrated under reduced pressure. The residue was purified bysilica gel column chromatography (a developing solvent ofchloroform/methanol=8/2) to obtain 3.0 parts of an Intermediate 3.

<Compound A-13>

The intermediate 3 (3 parts) and 0.7 parts of triethylamine weredissolved in 12 parts of methylene chloride, 4.6 parts of theintermediate 2 was added thereto, and the mixture was stirred at roomtemperature for 1 hour. To the obtained reaction solution was added 50parts of water to perform water-washing, and the reaction solution afterwater-washing was dried over magnesium sulfate and then purified bysilica gel column chromatography (a developing solvent ofchloroform/methanol=8/2) to obtain 0.8 parts of A-13.

<Synthesis of Dye Compound P-1>

2.7 parts of cyclohexanone was stirred at 90° C., and to the solutionwas added dropwise a solution obtained by adding 2 parts of A-13, 0.43parts of methacrylic acid, and V601 (0.42 parts) manufactured by WakoPure Chemical Industry Ltd. to 6.4 parts of cyclohexanone, for 1 hour.Then, the mixture was stirred at 90° C. for 3 hours. The obtainedreaction solution was left to be cooled to room temperature. Thereafter,this reaction solution was added dropwise to 100 parts of methanol. Theobtained crystal was separated by filtration, washed with 30 parts ofmethanol, and dried under reduced pressure at 40° C. to obtain 1.8 partsof P-1.

The dye compound P-1 was subjected to ¹H NMR spectrum measurement. Themeasurement was carried out using 400 MHz and dimethyl sulfoxide (DMSO).Product name: AV-400, manufactured by Bruker Co. Ltd., was used as ameasurement device. The measurement results are shown in FIG. 1.

<Synthesis Examples of Dye Compounds P-2 to P-44>

Dye compounds P-2 to P-44 were synthesized in the same manner as in thesynthesis of the dye compound P-1 except that the repeating unit in thedye compound P-1 was changed into those described in the followingtables.

The dye compounds P-25 and P-29 was subjected to ¹H NMR spectrummeasurement. The measurement was carried out using 400 MHz and dimethylsulfoxide (DMSO). Product name: AV-400, manufactured by Bruker Co. Ltd.,was used as a measurement device. The measurement results are shown inFIGS. 2 and 3.

As a comparative compound-1 to a Comparative compound-3, the followingcompounds were used.

TABLE 3 Dye compound Repeat- Repeat- Repeat- Repeat- (dye ing % by ing %by ing % by ing % by multimer) unit 1 mole unit 2 mole unit 3 mole unit4 mole Mw Mw/Mn λmax P-1 A′-13 25 B-1 75 — — — — 10600 1.85 538 P-2A′-14 30 B-1 35 B-18 35 — — 11000 1.88 532 P-3 A′-15 50 B-2 30 B-19 20 —— 15700 1.79 544 P-4 A′-16 30 B-1 40 B-18 30 — — 20100 1.82 531 P-5A′-17 20 B-1 30 B-19 50 — — 6700 1.86 538 P-6 A′-18 90 B-1 5 B-18 5 — —8800 1.81 533 P-7 A′-19 35 B-1 50 B-19 15 — — 24300 1.81 537 P-8 A′-2080 B-2 10 B-18 10 — — 7700 1.87 535 P-9 A′-21 10 B-1 50 A-14 40 — —13100 1.76 539 P-10 A′-22 50 B-1 50 — — — — 17800 1.83 541 P-11 A′-13 50B-1 40 B-8 10 — — 11900 1.87 538 P-12 A′-14 35 B-1 40 B-9 20 B-3 5 120001.78 532 P-13 A′-15 60 B-1 20 B-10 20 — — 17300 1.82 544 P-14 A′-16 25B-7 60 B-11 10 B-5 5 26300 1.85 531 P-15 A′-17 25 B-1 60 B-15 15 — —16100 1.88 538 P-16 A′-18 70 B-1 10 B-16 15 B-7 5 13200 1.81 533 P-17A′-19 30 B-1 60 B-17 10 — — 24100 2 537 P-18 A′-20 70 B-7 20 B-22 10 — —7800 1.95 535 P-19 A′-21 20 B-1 60 B-21 20 — — 10600 1.89 539 P-20 A′-2240 B-1 40 B-23 20 — — 18400 1.92 541 P-21 A′-23 25 B-1 60 B-18 15 — —6800 1.93 P-22 A′-24 25 B-2 60 B-19 15 — — 14000 1.84 P-23 A′-25 25 B-360 B-20 15 — — 13500 1.83 P-24 A′-26 25 B-4 60 B-21 15 — — 9800 1.94P-25 A′-27 20 B-1 40 B-26 10 B-18 30 14200 1.84 538 P-26 A′-28 20 B-1 40B-27 10 B-18 30 12100 1.95 532 P-27 A′-29 20 B-1 40 B-27 10 B-18 3012700 1.86 533 P-28 A′-30 25 B-2 20 B-24 20 B-18 35 14800 1.82 531 P-29A′-31 20 B-1 40 B-26 10 B-33 30 15500 1.87 531 P-30 A′-31 20 B-1 40 B-2610 B-33 30 8300 1.91 531 P-31 A′-32 30 B-1 35 B-25 5 B-18 30 9800 1.97539 P-32 A′-33 28 B-1 20 B-28 22 B-33 30 15700 1.93 537 P-33 A′-34 15B-7 30 B-29 5 B-18 47 10300 1.79 530 P-34 A′-35 22 B-1 25 B-30 15 B-1838 11900 1.85 537 P-35 A′-36 15 B-1 30 B-31 5 B-19 50 8900 1.88 541 P-36A′-37 18 B-1 30 B-32 25 B-18 27 10100 1.95 541 P-37 A′-36 20 B-1 25 B-2625 B-18 30 9100 1.83 541 P-38 A′-37 20 B-1 40 B-26 10 B-18 30 17500 1.92541 P-39 A′-14 20 B-1 40 B-26 10 B-33 30 7800 1.86 532 P-40 A-pm-1 20B-1 40 B-18 40 — — 12050 1.88 P-41 sm-3 20 B-1 40 B-18 40 — — 11500 1.94P-42 A-PM-1 20 B-1 40 B-18 40 — — 11300 1.95 P-43 A′-38 20 B-1 40 B-1840 — — 10400 1.92 555 P-44 A′-39 20 B-1 40 B-18 40 — — 10200 1.96 548

Synthesis Examples of Intermediate 4

10 parts of DCSF (manufactured by Chugai Kasei Co Ltd.), 10.5 parts of2,6-diisopropylaniline, and 40 parts of sulfolane were put into a flaskand the mixture was stirred at an internal temperature of 80° C. for 5hours. Thereafter, 33.2 parts of 2,6-diisopropylaniline and 3.88 partsof magnesium chloride were added to the reaction solution, and themixture was stirred at 125° C. for 48 hours. The obtained reactionsolution was left to be cooled to room temperature and added dropwise to400 parts of 2 N hydrochloric acid, and the precipitated crystal wasseparated by filtration. The crystal was dispersed in and washed with200 parts of acetonitrile, collected by filtration, and air-dried for 10hours to obtain 12 parts (yield: 70.8%) of an intermediate 4.

Synthesis Examples of Intermediate 5

An intermediate 5 was synthesized by the same procedure as for theintermediate 2 except that the intermediate 4 was used instead of theintermediate 1 used in the synthesis of the intermediate 2.

Synthesis Example of Dye Compound (A-40)

A dye compound (A-40) was synthesized by the same procedure as for thedye compound (A-1) except that the intermediate 5 was used instead ofthe intermediate 2 used in the synthesis of the dye compound (A-1).

Synthesis Example of Dye Compound A-41

A dye compound (A-41) was synthesized by the same procedure as for thedye compound (A-40) except that DCSF which is a raw material for the dyecompound (A-40) was changed to fluorescein chloride.

Synthesis Example of Dye Compound A-42

The synthesis was carried out by the same procedure as for the dyecompound (A-40) except that pentafluorobenzene sulfonylamide was usedinstead of trifluoromethane sulfonylamide used for the synthesis of thedye compound (A-40). The pentafluorobenzene sulfonylamide wassynthesized by, for example, the method described in Bioorganic andMedicinal Chemistry, 2013, vol. 21, #7 p. 2093 to 2106.

The dye compound A-42 was subjected to 1H NMR spectrum measurement. Themeasurement was carried out using 400 MHz and dimethyl sulfoxide (DMSO).Product name: AV-400, manufactured by Bruker Co. Ltd., was used as ameasurement device.

δ 0.93-1.35 (24H, m), 2.85-3.13 (4H, m), 5.98-6.28 (2H, m), 7.02-7.43(11H, m), 7.44-8.28 (3H, m), 9.87-10.08 (2H, m).

Synthesis Example of Dye Compound A-43

The synthesis was carried out by the same procedure as for the dyecompound (A-40) except that benzene sulfonylamide was used instead oftrifluoromethane sulfonylamide used for the synthesis of the dyecompound (A-40) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) was usedinstead of triethylamine.

The dye compound A-43 was subjected to ¹H NMR spectrum measurement. Themeasurement was carried out using 400 MHz and dimethyl sulfoxide (DMSO).Product name: AV-400, manufactured by Bruker Co. Ltd., was used as ameasurement device.

δ 0.9-1.34 (24H, m), 2.87-3.18 (4H, m), 5.88-6.14 (2H, m), 7.07-7.53(16H, m), 7.53-8.21 (3H, m), 9.88-10.04 (2H, m).

Synthesis Example of Dye Compound A-44

3 parts of the dye compound (A-48) and 15 parts of N,N-dimethylacetamidewere put into a 3-neck flask, and the mixture was stirred at roomtemperature. 0.3 parts of acrylic acid chloride was added dropwisethereto and the mixture was stirred at room temperature for 1 hour.Thereafter, the reaction solution was added dropwise to 100 parts of 1 Maqueous hydrochloric acid and the obtained crystal was separated byfiltration. The crystal was washed with 50 parts of acetonitrile, andafter filtration, the obtained crystal was dried for 10 hours using anair dryer set to 40° C. to obtain 3 parts (yield 95%) of a dye compound(A-44).

The dye compound A-44 was subjected to ¹H NMR spectrum measurement. Themeasurement was carried out using 400 MHz and dimethyl sulfoxide (DMSO).Product name: AV-400, manufactured by Bruker Co. Ltd., was used as ameasurement device.

δ 0.94-1.34 (24H, m), 2.82-3.14 (6H, m), 4.24-4.29 (2H, t), 5.76-6.14(7H, m), 7.04-7.53 (8H, m), 7.54-8.16 (4H, m), 9.88-10.06 (2H, m).

Synthesis Example of Dye Compound A-45

150 parts of pentafluorobenzene sulfonylamide, 49.8 parts of2-mercaptoethanol, and 1000 parts of methanol were added to a 3-neckflask, and the mixture was stirred at room temperature. 64.5 parts oftriethylamine was added dropwise thereto and the mixture was stirred atroom temperature for 1 hour. Methanol was concentrated under reducedpressure and the residue was extracted by the addition of 900 parts ofethyl acetate, 900 parts of saturated physiologicalsaline, and 100 partsof a saturated aqueous sodium hydrogen carbonate solution. The organiclayer was dried over magnesium sulfate and then the filtrate obtained byfiltration was concentrated to obtain 169 parts (yield 91%) of2,3,5,6-tetrafluoro-4-((2-hydroxyethyl)thio)benzenesulfonamide.

50 parts of2,3,5,6-tetrafluoro-4-((2-hydroxyethyl)thio)benzenesulfonamide, 165parts of N,N-dimethylacetamide, 28 parts of 2-isocyanatoethylmethacrylate (Karenz MOI manufactured by Showa Denko K. K.), and 0.01parts of Neostann U-600 (manufactured by Chemical Industry Co., Ltd.)were put into to a 3-neck flask, and the mixture was stirred at 60° C.for 2 hours. The reaction liquid was left to be cooled to roomtemperature and then subjected to liquid separation with 600 parts ofethyl acetate and 600 parts of water. The organic layer was dried overmagnesium sulfate and the filtrate obtained by filtration wasconcentrated under reduced pressure. To the obtained residue was added200 parts of chloroform and the mixture was stirred. The obtainedcrystal was filtered and air-dried at 40° C. for 10 hours to obtain 62.3parts (yield 86%) of3-(((2-((2,3,5,6-tetrafluoro-4-sulfamoylphenyl)thio)carbonyl)amino)propylmethacrylate.

A dye compound (A-45) was synthesized by the same procedure as for thedye compound (A-40) except that3-(((2-((2,3,5,6,-tetrafluoro-4-sulfamoylphenyl)thio)carbonyl)amino)propylmethacrylate was used instead of trifluoromethane sulfonylamide used forthe synthesis of the dye compound (A-40).

The dye compound A-45 was subjected to ¹H NMR spectrum measurement. Themeasurement was carried out using 400 MHz and dimethyl sulfoxide (DMSO).Product name: AV-400, manufactured by Bruker Co. Ltd., was used as ameasurement device.

δ 0.95-1.35 (24H, m), 1.84-1.9 (3H, s), 2.85-3.15 (4H, m), 3.15-3.3 (4H,m), 4.0-4.18 (4H, m), 5.62-6.18 (4H, m), 7.03-7.43 (11H, m), 7.43-8.18(3H, m), 9.89-10.08 (2H, m).

Synthesis Example of Dye Compound A-46

The synthesis was carried out in the same manner as for the dye compound(A-13) except that the intermediate 2 which is a raw material for thedye compound (A-13) was changed to the intermediate 5.

The dye compound A-46 was subjected to ¹H NMR spectrum measurement. Themeasurement was carried out using 400 MHz and dimethyl sulfoxide (DMSO).Product name: AV-400, manufactured by Bruker Co. Ltd., was used as ameasurement device.

δ 0.95-1.38 (24H, m), 2.83-3.12 (4H, m), 5.33-5.39 (1H, d), 5.85-6.16(3H, m), 6.73-7.52 (14H, m), 7.6-7.68 (2H, m), 7.7-7.9 (3H, m),9.9-10.08 (2H, m).

Synthesis Example of Dye Compound A-47

20 parts of dye compound (A-42), 3.08 parts of 6-mercaptohexanol, and 70parts of N,N-dimethyl formamide were added to a 3-neck flask and themixture was stirred in an ice bath. 11 parts of DBU was added dropwisethereto and the mixture was at room temperature for 30 minutes. Themixture was extracted with 200 parts of 1 M aqueous hydrochloric acidand 300 parts of ethyl acetate, and then extracted with 400 parts ofwater. Then, the organic layer was dried over magnesium sulfate and thenthe filtrate obtained by filtration was concentrated under reducedpressure. To the residue was added 80 parts of acetonitrile and themixture was stirred at 70° C. for 1 hour and then filtered. The obtainedcrystal was air-dried at 40° C. for 10 hours to obtain 18 parts (yield80%) of an analogous intermediate of the dye compound (A-54).

52 parts of the analogous intermediate of the dye compound (A-54) and390 parts of pyridine were put into to a 3-neck flask and the mixturewas stirred in an ice bath, and 28.8 parts of tosyl chloride wasdividedly added in the form of powder. Thereafter, the mixture wassubjected to liquid separation with 600 parts of 2 M aqueoushydrochloric acid and 400 parts of chloroform, pyridine was extractedfrom the organic layer, followed by liquid separation with 600 parts ofa saturated aqueous sodium hydrogen carbonate solution, the organiclayer was dried over magnesium sulfate, and the filtrate obtained byfiltration was concentrated. To the residue was added 500 parts ofacetonitrile and the mixture was stirred under heating and refluxing andfiltered, and the obtained crystal was air-dried at 40° C. for 10 hoursto obtain 51 parts (yield 85.3%) of a dye compound (A-47).

The dye compound A-47 was subjected to ¹H NMR spectrum measurement. Themeasurement was carried out using 400 MHz and dimethyl sulfoxide (DMSO).Product name: AV-400, manufactured by Bruker Co. Ltd., was used as ameasurement device.

δ 0.95-1.33 (28H, m), 1.33-1.55 (4H, m), 2.83-3.12 (6H, m), 4.0-4.04(2H, m), 5.89-6.14 (2H, m), 7.01-7.82 (17H, m), 8.06-8.17 (1H, m),9.9-10.08 (2H, m).

Synthesis Example of Dye Compound A-48

The synthesis was carried out by the same procedure as the synthesis ofthe analogous intermediate of the dye compound (A-54) except that the6-mercaptohexanol used for the synthesis of the analogous intermediateof the dye compound (A-54) described in Synthesis Example of the dyecompound (A-47) was changed to 2-mercaptoethanol.

The dye compound A-48 was subjected to ¹H NMR spectrum measurement. Themeasurement was carried out using 400 MHz and dimethyl sulfoxide (DMSO).Product name: AV-400, manufactured by Bruker Co. Ltd., was used as ameasurement device.

δ 0.95-1.36 (24H, m), 2.83-3.15 (6H, m), 3.45-3.58 (3H, m), 5.89-6.14(2H, m), 7.01-7.55 (11H, m), 7.63-8.17 (3H, m), 9.95-10.09 (2H, m).

Synthesis Example of Dye Compound A-49

The synthesis was carried out by the same procedure as the synthesis ofthe analogous intermediate of the dye compound (A-54) except that the6-mercaptohexanol used for the synthesis of the analogous intermediateof the dye compound (A-54) described in Synthesis Example of the dyecompound (A-47) was changed to 1,6-hexanedithiol.

Synthesis Example of Dye Compound A-50

A dye compound (A-50) was obtained by adding tetrabutylammonium chlorideto the dye compound (A-47) and substituting a tosyl group with achloride ion.

Synthesis Example of Dye Compound A-51

A dye compound (A-51) was obtained by adding potassium phthalimide tothe dye compound (A-47) or the dye compound (A-50) and using the methoddescribed in Chem. Eur. J. 2010, 16, 10021 to 10029 for protection withhydrazine.

Synthesis Example of Dye Compound A-52

The synthesis was carried out by the same procedure as for the dyecompound (A-40) except that methane sulfonylimide was used instead oftrifluoromethane sulfonylamide used for the synthesis of the dyecompound (A-40) and DBU was used instead of triethylamine.

The dye compound A-52 was subjected to ¹H NMR spectrum measurement. Themeasurement was carried out using 400 MHz and dimethyl sulfoxide (DMSO).Product name: AV-400, manufactured by Bruker Co. Ltd., was used as ameasurement device.

δ 0.96-1.36 (24H, m), 2.58-2.64 (3H, s), 2.85-3.15 (4H, m), 5.91-6.14(2H, m), 7.07-7.52 (11H, m), 7.58-8.22 (3H, m), 9.85-10.04 (2H, m).

Synthesis Example of Dye Compound A-53

The synthesis was carried out by the same procedure as the synthesis ofthe analogous intermediate of the dye compound (A-54) except that the6-mercaptohexanol used for the synthesis of the analogous intermediateof the dye compound (A-54) described in Synthesis Example of the dyecompound (A-47) was changed to 4-mercaptobutyric acid.

Synthesis Example of Dye Compound A-54

The synthesis was carried out by the same procedure as the synthesis ofthe analogous intermediate of the dye compound (A-54) except that the6-mercaptohexanol used for the synthesis of the analogous intermediateof the dye compound (A-54) described in Synthesis Example of the dyecompound (A-47) was changed to 2-(3-mercaptopropoxy)ethanol.

The dye compound A-54 was subjected to ¹H NMR spectrum measurement. Themeasurement was carried out using 400 MHz and dimethyl sulfoxide (DMSO).Product name: AV-400, manufactured by Bruker Co. Ltd., was used as ameasurement device.

δ 0.96-1.36 (26H, m), 1.63-1.8 (2H, m), 2.83-3.11 (6H, m), 3.4-3.5 (4H,m), 4.46-4.55 (1H, s), 5.84-6.17 (2H, m), 6.93-7.53 (11H, m), 7.63-8.18(3H, m), 9.85-10.15 (2H, br).

Synthesis Example of Dye Compound A-55

The synthesis was carried out by the same procedure as the synthesis ofthe dye compound (A-45) except that the 2-isocyanatoethyl methacrylate(Karenz MOI manufactured by Showa Denko K. K.) used for the synthesis ofthe dye compound (A-45) was changed to 2-isocyanatoethyl acrylate(Karenz AOI manufactured by Showa Denko K. K.).

The dye compound A-55 was subjected to ¹H NMR spectrum measurement. Themeasurement was carried out using 400 MHz and dimethyl sulfoxide (DMSO).Product name: AV-400, manufactured by Bruker Co. Ltd., was used as ameasurement device.

δ 0.95-1.35 (24H, m), 2.85-3.15 (4H, m), 3.15-3.28 (4H, m), 4.0-4.16(4H, m), 5.88-6.36 (5H, m), 7.03-7.54 (11H, m), 7.63-8.18 (3H, m),9.91-10.08 (2H, m).

TABLE 4 Dye compound [M + H]+ λmax (nm) A-40 818.3 540 A-41 782.3 526A-42 916.3 528 A-43 826.3 527 A-44 1028.3 531 A-45 1129.3 531 A-461082.3 538 A-47 1184.4 531 A-48 974.3 531 A-49 1046.3 531 A-50 1048.3531 A-51 1029.3 531 A-52 763.31 527 A-53 1016.3 531 A-54 1032.3 531 A-551115.3 531 A-1 706.2 535

Examples and Comparative Examples

1. Preparation of Resist Solution

Components having the following composition were mixed and dissolved toprepare a resist solution for an undercoat layer.

<Composition of Resist Solution for Undercoat Layer>

Solvent: propylene glycol monomethyl ether acetate 19.20 parts Solvent:ethyl lactate 36.67 parts Alkali-soluble resin: 40% PGMEA solution ofbenzyl 30.51 parts methacrylate/methacrylic acid/2-hydroxyethylmethacrylate copolymer (molar ratio = 60/22/18, weight-average molecularweight of 15,000, number- average molecular weight of 9,000)Ethylenically unsaturated double bond-containing 12.20 parts compound:dipentaerythritol hexaacrylate Polymerization inhibitor: p-methoxyphenol0.0061 parts Fluorine-based surfactant: F-475, manufactured by 0.83parts DIC Corporation Photopolymerization initiator: trihalomethyl 0.586parts triazine-based photopolymerization initiator (TAZ-107 manufacturedby Midori Kagaku Co., Ltd.)

2. Manufacture of Undercoat Layer-Attached Silicon Wafer Substrate

A 6-inch silicon wafer was heated in an oven at 200° C. for 30 minutes.Next, the resist solution was applied onto this silicon wafer such thatthe dry film thickness became 1.5 μm. Further, the resultant was furtherheated and dried in an oven at 220° C. for 1 hour to form an undercoatlayer, thereby obtaining an undercoat layer-attached silicon wafersubstrate.

3. Preparation of Colored Composition

3-1. Preparation of Blue Pigment Dispersion

<Preparation of Blue Pigment Dispersion P1>

A blue pigment dispersion P1 was prepared in the following manner.

A mixed solution consisting of 13.0 parts (blue pigment, averageparticle size of 55 nm) of C. I. Pigment Blue 15:6 (blue pigment,hereinafter referred to as “PB 15:6”), 5.0 parts of Disperbyk111 as apigment dispersant, and 82.0 parts of PGMEA was mixed and dispersed for3 hours by a beads mill (zirconia beads having a diameter of 0.3 mm) toprepare a pigment dispersion. Thereafter, the pigment dispersion wasfurther subjected to a dispersion treatment under a pressure of 2000kg/cm³ and at a flow rate of 500 g/min, by using a high-pressuredispersing machine equipped with a depressurizing mechanism.NANO-3000-10 (manufactured by Nihon B.E.E Co., Ltd.). This dispersiontreatment was repeated 10 times to obtain a blue pigment dispersion P1(a dispersion of C. I. Pigment Blue 15:6, pigment concentration of 13%)used in the colored compositions of Examples or Comparative Examples.

For the obtained blue pigment dispersion P1, the particle size of thepigment was measured using a dynamic light scattering method (MicrotracNanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)), and as aresult, was found to be 24 nm.

In the same manner as the preparation of the blue pigment dispersion P1except that a combination of a pigment shown below and dispersant resinagent, Disperbyk111, was used instead of a combination of C. I. PigmentBlue 15:6 used as a blue pigment in the blue pigment dispersion P1 and adispersant resin agent, Disperbyk111 in “3-1. Preparation of BluePigment Dispersion”, a red pigment dispersion, a green pigmentdispersion, and a yellow pigment dispersion were prepared.

Pigment for a red pigment dispersion: C. I. Pigment Red 246 (PR246)

Pigment for a yellow pigment dispersion: C. I. Pigment Yellow 139(PY139)

Pigment for a green pigment dispersion: C. I. Pigment Green 58 (PG58)

<Preparation of Blue Pigment Dispersion P2>

A mixed solution consisting of 19.4 parts by mass of PB 15:6 (averageprimary particle size of 55 nm), 2.95 parts by mass of a dispersantresin agent BYK-161 (manufactured by BYK-Chemie), 2.95 parts by mass interms of solid contents (9.93 parts by mass of a solution) of analkali-soluble resin 1 (a copolymer of benzyl methacrylate/methacrylicacid, 30% PGMEA solution), and 165.3 parts by mass of PGMEA was mixedand dispersed for 3 hours by using a beads mill (zirconia beads having adiameter of 0.3 mm). Thereafter, the mixed solution was furthersubjected to a dispersing treatment under a pressure of 2000 kg/cm³ andat a flow rate of 500 g/min by using a depressurizing mechanism-attachedhigh-pressure dispersing machine NANO-3000-10 (manufactured by NihonB.E.E Co., Ltd.). The dispersing treatment was repeated 10 times,thereby obtaining a PB 15:6 dispersion as a pigment dispersion. For theobtained PB 15:6 dispersion, the average primary particle size of thepigment was measured using a dynamic light scattering method (MicrotracNanotrac UPA-EX150 manufactured by Nikkiso Co., Ltd.) and found to be 24nm.

<Preparation of Blue Pigment Dispersion P3>

A blue pigment dispersion P2 was prepared by the same method as inPreparation of Blue Pigment Dispersion P2 above except that thefollowing dispersant resin agent D1 was used as a dispersant resinagent.

Dispersant Resin Agent D1

The acid value of the dispersant resin agent D1 was 100 mgKOH/g.Further, the weight average molecular weight of the dispersant resinagent D1 was 20000. Further, the mass ratio of x to y in the structureof the dispersant resin agent D1 was 50:50 and n was 20.

<Preparation of Blue Pigment Dispersion P4>

A blue pigment dispersion P4 was prepared by the same method as inPreparation of Blue Pigment Dispersion P2 above except that thefollowing dispersant resin agent D2 was used as a dispersant resinagent.

The acid value of the dispersant resin agent D2 was 100 mgKOH/g.Further, the weight average molecular weight of the dispersant resinagent D2 was 20000. Further, the mass ratio of x to y in the structureof the dispersant resin agent D2 was 15:85 and n was 20.

<Preparation of Blue Pigment Dispersion P5>

A pigment dispersion P5 was prepared by the same method as the pigmentdispersion P2 except in Preparation of Blue Pigment Dispersion P2 abovethat C. I. Pigment Red 254 was used instead of PB 15:6 as a pigment. Theaverage primary particle size of the pigment (C. I. Pigment Red 254) wasmeasured using a dynamic light scattering method (Microtrac NanotracUPA-EX 150 manufactured by Nikkiso Co., Ltd.) and found to be 26 nm.

3-2. Preparation of Colored Composition

Colored Compositions of Examples 1 to 27 and Comparative Examples 1 to 3

The following respective components were mixed and dissolved to obtainthe respective colored compositions of Examples and ComparativeExamples.

Dye compound (A) (the compound described in the 0.04 parts followingtable) in terms of a solid content Solvent (PGMEA) 1.133 partsAlkali-soluble resin (J1 or J2 shown below) 0.03 parts Dispersant(Solsperse 20000: (1% cyclohexane solution, 0.125 parts manufactured byThe Lubrizol Corporation)) Photopolymerization initiator (compounds ofC-4 to 0.012 parts C-13 below) Pigment dispersion P1 (pigmentconcentration of 13%) 0.615 parts Curable compound 0.07 parts Surfactant(glycerol propoxylate: (1% cyclohexane 0.048 parts solution))

Colored Compositions of Examples 28 to 93 and Comparative Examples 4 to6

The following respective components were mixed and dissolved to obtainthe respective colored compositions of Examples and ComparativeExamples.

Solvent (cyclohexanone) 17.12 parts Alkali-soluble resin 1 (a copolymerof benzyl 1.23 parts methacrylate (BzMA) and methacrylic acid (MAA), 30%PGMEA solution) Alkali-soluble resin 2 (ACRYCURE-RD-F8 0.23 parts(manufactured by Nippon Shokubai Co., Ltd.)) Photopolymerizationinitiator I-2 (IRGACURE OXE-02) 0.975 parts Cyclohexanone solution ofdye multimer (solid content 24.57 parts concentration of 12.3%) Pigmentdispersion (solid content concentration of 51.40 parts 12.8%) Curablecompound 1.96 parts Polymerization inhibitor (p-methoxyphenol) 0.0007parts Photopolymerization inhibitor (p-methoxyphenol) Fluorine-basedsurfactant (F475 manufactured by DIC 2.50 parts Corporation, 1% PGMEAsolution)

Curable compound dipentaerythritol hexaacrylate (manufactured byShin-Nakamura Chemical Co., Ltd.)

NK Ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.)

KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.)

Polyfunctional thiol compound (chain transfer agent): compounds of thefollowing S-1 to S-5

Epoxy Compounds

E-1: EHPE3150, manufactured by Daicel Chemical Industries, Ltd.

E-2: EPICLON 840 (manufactured by DIC Corporation)

E-3: EPICLON N660 (manufactured by DIC Corporation)

E-4: EPICLON HP7200 (manufactured by DIC Corporation)

4. Manufacture of Color Filter Using Colored Composition

<Manufacture of Color Filter Using Colored composition byPhotolithography>

<<Pattern Formation>>

Each of the colored compositions of Examples and Comparative Examples,which had been prepared as above, was applied onto the undercoat layerof the undercoat layer-attached silicon wafer substrate obtained in theabove section 2, thereby forming a colored composition layer (coatingfilm). Then, a heating treatment (pre-baking) was carried out for 120seconds by using a hot plate at 100° C. such that the dry film thicknessof the coating film became 0.6 μm.

Next, by using an i-ray stepper exposure device FPA-3000i5+(manufactured by CANON Inc.), the wafer was exposed at a wavelength of365 nm through an island pattern mask having a 1.0 μm×1.0 μm pattern, byvarying the exposure dose in a range from 50 mJ/cm² to 1200 mJ/cm².

Subsequently, the silicon wafer substrate, which had been irradiatedwith light and had a coating film formed thereon, was loaded onto ahorizontal spin table of a spin shower developing machine (Model DW-30,manufactured by Chemitronics Co., Ltd.), and subjected to paddledevelopment at 23° C. for 60 seconds by using CD-2000 (manufactured byFUJIFILM Electronic Materials CO., LTD.), thereby forming a coloredpattern on the silicon wafer substrate.

The silicon wafer on which the colored pattern had been formed was fixedonto the horizontal spin table by a vacuum chuck method, and the siliconwafer substrate was rotated at a rotation frequency of 50 r.p.m. byusing a rotation device. In this state, from the position above therotation center, pure water was supplied onto the wafer from a spraynozzle in the form of shower so as to perform rinsing treatment, andthen the wafer was spray-dried.

In the manner described above, a monochromic color filter having thecolored pattern formed of the colored compositions of Examples orComparative Examples were manufactured.

Thereafter, the size of the colored pattern was measured by using alength measuring SEM “S-9260A” (manufactured by Hitachi. Ltd.). Anexposure dose at which the pattern size became 1.0 μm was determined asan optimal exposure dose.

<Manufacture of Color Filter Using Colored Curable Composition by DryEtching Method>

A colored layer was manufactured by applying he colored compositions ofExamples and Comparative Examples, which had been prepared as above,onto a 7.5 cm×7.5 cm glass substrate using a spin coater such that thefilm thickness became 0.5 μm, followed by heating at 200° C. for 5minutes using a hotplate, and curing the coating film. The filmthickness of the colored layer was 0.5 μm.

Subsequently, a positive type photoresist “FHi622BC” (manufactured byFUJIFILM Electronic Materials Co., Ltd.) was applied and subjected to apre-baking treatment at 90° C. for 1 minute to form a photoresist layerhaving a film thickness of 0.8 μm.

Next, the photoresist layer was patternwise exposed at an exposure doseof 350 mJ/cm² using an i-ray stepper (manufactured by Canon Inc.) andthen subjected to a heating treatment at a photoresist layer temperatureor the atmospheric temperature of 90° C. for 1 minute. Thereafter, adeveloping treatment was carried out for 1 minute with a developer“FHD-5” (manufactured by FUJIFILM Electronic Materials Co., Ltd.) andfurther subjected to a post-baking treatment at 110° C. for 1 minute toform a resist pattern. The size of the resist pattern was formed at 1.0μm on one side, in consideration of the etching conversion difference(reduction in the pattern width due to etching).

Subsequently, the glass substrate after resist pattern formation wasadhered to an 8-inch silicon wafer and subjected to a first stageetching treatment for 80 seconds with a dry etching apparatus (U-621,manufactured by Hitachi High-Technologies Corporation) under conditionsof an RF power: 800 W, an antenna bias: 400 W, a wafer bias: 200 W, theinternal pressure of the chamber: 4.0 Pa, a substrate temperature: 50°C., and the gas kind and the flow rate of a mixed gas: CF₄: 80 ml/min.,O₂: 40 mL/min., and Ar: 800 mL/min.

Next, a second stage etching treatment, that is, an over-etchingtreatment, was carried out for 28 seconds using the same etching chamberunder conditions of an chamber RF power 600 W, an antenna bias: 100 W, awafer bias: 250 W, the internal pressure of a chamber: 2.0 Pa, asubstrate temperature: 50° C., and the gas kind and the flow rate of amixed gas: N₂: 500 mL/min., O₂: 50 mL/min., and Ar: 500 mL/min(N₂/O₂/Ar=10/1/10).

After carrying out dry etching under the above conditions, the resistwas removed by performing a peeling process for 120 seconds at 50° C.using a photoresist peeling solution “MS230C” (manufactured by FUJIFILMElectronic Materials Co., Ltd.), and a green color pattern was formed.Washing with pure water and spin drying were further performed, andthereafter a dehydration baking process was performed for 2 minutes at100° C., thereby obtaining a color filter.

5. Evaluation of Performance

5-1. Heat Resistance

The glass substrate on which the colored composition obtained above hadbeen applied was loaded onto a hot plate at 200° C. such that it cameinto contact with the substrate surface, and was heated for 1 hour.Then, the color difference (ΔE*ab value) before and after the heatingwas measured using a colorimeter MCPD-1000 (manufactured by OtsukaElectronics Co., Ltd.), and used as an index for evaluating the heatfastness, and the index was evaluated in accordance with the followingevaluation criteria. A smaller ΔE*ab value indicates better heatresistance. Incidentally, the ΔE*ab value is a value determined from thefollowing color-difference formula according to CIE 1976 (L*, a*, b*)color space (New Edition of Color Science Handbook (1985) p. 266, editedby The Color Science Association of Japan).

ΔE*ab={(ΔL*)2+(Δa*)2+(Δb*)2}½ was evaluated under the followingcriteria.

A: The value of ΔE*ab value is 0 or more and less than 1.0.

B: The value of ΔE*ab value is 1.0 or more and less than 3.0.

C: The value of ΔE*ab value is 3.0 or more.

5-2. PGMEA Solubility

The solvent solubility of the obtained colored composition with respectto PGMEA was evaluated in accordance with the following criteria.

A: A case showing a solubility of 20% by mass or more.

B: A case showing a solubility of 10% by mass or more and less than 20%by mass.

C: A case showing a solubility of 5% by mass or more and less than 10%by mass.

D: A case showing a solubility of less than 5% by mass.

5-3. Cyclohexanone Solubility

The solvent solubility of the obtained colored composition with respectto cyclohexanone was evaluated in accordance with the followingcriteria.

A: A case showing a solubility of 20% by mass or more.

B: A case showing a solubility of 10% by mass or more and less than 20%by mass.

C: A case showing a solubility of 5% by mass or more and less than 10%by mass.

D: A case showing a solubility of less than 5% by mass.

5-4. Evaluation of Color Migration

The absorbance of the colored pattern in each of the color filters wasmeasured by MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.)(Absorbance A).

A CT-2000L solution (a transparent undercoating agent, manufactured byFUJIFILM Electronics Materials Co., Ltd.) was applied onto the surface,on which the colored pattern of the color filter had been formed, suchthat the dried film thickness became 1 μm, and dried to form atransparent film, and the film was subjected to a heating treatment at280° C. for 5 minutes.

After the completion of heating, the absorbance of the transparent filmadjacent to the colored pattern was measured by MCPD-3000 (manufacturedby Otsuka Electronics Co., Ltd.) (Absorbance B).

The ratio [%] of the absorbance B value of the obtained transparent filmto the absorbance A value of the colored pattern which had been measuredbefore heating was calculated [the following (Equation A)]. The ratiowas used as an index for evaluating the color migration to adjacentpixels.

Color migration (%)=Absorbance B/Absorbance A×100  (Equation A)

A: The value of Equation A is 0 or more and less than 2.

B: The value of Equation A is 2 or more and less than 5.

C: The value of Equation A is 5 or more.

5-5. Spectral Evaluation before and after Development

A CT-4000L solution (a transparent undercoating agent, manufactured byFUJIFILM Electronic Materials Co., Ltd.) was applied onto a glass wafersuch that the dry film thickness became 0.1 μm and dried to form atransparent film, and the film was subjected to a heating treatment at220° C. for 5 minutes.

The colored composition was applied using a spin coater such that thefilm thickness became 0.6 μm, and then subjected to a heating treatment(pre-baking) by using a hotplate at 100° C. for 120 seconds.

Next, the coating film was exposed at an exposure dose of 500 mJ/cm² ata wavelength of 365 nm using an i-ray stepper exposure apparatusFPA-3000i5+(manufactured by Canon Inc.).

The transmittance of the color filter thus obtained at a wavelengthregion from 300 nm to 800 nm was measured by using anultraviolet-visible near-infrared spectrophotometer UV3600 (manufacturedby Shimadzu Corporation) as a spectrophotometer (reference glasssubstrate).

The color filter which had been subjected to transmittance measurementwas placed on a horizontal turntable of a spin shower developmentmachine (model DW-30, manufactured by Chemtronics Co., Ltd.) andsubjected to puddle development at 23° C. for 60 seconds by usingCD-2000 (manufactured by FUJIFILM Electronics Materials Co., Ltd.).While the silicon wafer substrate was rotated by a rotation device at arotation number of 50 r.p.m., pure water was supplied by showering froman ejection nozzle above the rotation center to carry out a rinsetreatment, followed by spray-drying. After drying, a spectralmeasurement was carried out again to evaluate a change in thetransmittance between before and after development (a value representedby an equation of |T0−T1| in the case where the transmittance beforedevelopment is defined as T0 and the transmittance after development isT1).

AA: Good. A case where the change in the transmittance before and afterdevelopment is less than 2% in the entire region ranging from 300 nm to800 nm.

A: Satisfactory. A case where the change in the transmittance before andafter development is 2% or more and less than 5% in the entire regionranging from 300 nm to 800 nm.

B: Sufficient. A case where the change in the transmittance before andafter development is 5% or more and less than 10% in the entire regionranging from 300 nm to 800 nm.

C: Insufficient. A case where the change in the transmittance before andafter development is 10% or more in the entire region ranging from 300nm to 800 nm.

TABLE 5 Method for Dye Curable Photopoly- Alkali- manufacturing compoundcompound Solvent Pigment merization soluble color filter (A) (B) (C)dispersion initiator resin Example 1 Photolithography A-1Dipentaerythritol PGMEA P1 C-4 J1 hexaacrylate Example 2Photolithography A-2 Dipentaerythritol PGMEA P1 C-5 J1 hexaacrylateExample 3 Photolithography A-13 Dipentaerythritol PGMEA P1 C-4 J1hexaacrylate Example 4 Photolithography P-1 Dipentaerythritol PGMEA/ P1C-9 J1 hexaacrylate cyclo- hexanone = 60/40 Example 5 PhotolithographyP-2 Dipentaerythritol PGMEA P1 C-7 J1 hexaacrylate Example 6Photolithography P-3 Dipentaerythritol PGMEA P1 C-13 J1 hexaacrylateExample 7 Photolithography P-4 Dipentaerythritol PGMEA P1 C-9 J1hexaacrylate Example 8 Photolithography P-5 Dipentaerythritol PGMEA P1C-10 J1 hexaacrylate Example 9 Photolithography P-6 DipentaerythritolPGMEA/ P1 C-11 J1 hexaacrylate cyclo- pentanone = 70/30 Example 10Photolithography P-7 Dipentaerythritol PGMEA P1 C-12 J1 hexaacrylateExample 11 Photolithography P-8 Dipentaerythritol PGMEA P1 C-13 J1hexaacrylate Example 12 Photolithography P-9 Dipentaerythritol PGMEA P1C-4 J1 hexaacrylate Example 13 Photolithography P-10 DipentaerythritolPGMEA P1 C-9 J1 hexaacrylate Example 14 Photolithography P-11Dipentaerythritol PGMEA/ P1 C-5 J1 hexaacrylate cyclo- pentanone = 50/50Example 15 Photolithography P-12 Dipentaerythritol PGMEA P1 C-13 J1hexaacrylate Example 16 Photolithography P-13 Dipentaerythritol PGMEA P1C-10 J1 hexaacrylate Example 17 Photolithography P-14 DipentaerythritolPGMEA P1 C-8 J1 hexaacrylate Example 18 Photolithography P-15Dipentaerythritol PGMEA P1 C-6 J1 hexaacrylate Example 19Photolithography P-16 Dipentaerythritol PGMEA P1 C-11 J1 hexaacrylateExample 20 Photolithography P-17 Dipentaerythritol PGMEA P1 C-9 J1hexaacrylate Example 21 Photolithography P-18 Dipentaerythritol PGMEA P1C-12 J1 hexaacrylate Example 22 Photolithography P-19 DipentaerythritolPGMEA P1 C-10 J1 hexaacrylate Example 23 Photolithography P-20Dipentaerythritol PGMEA P1 C-4 J1 hexaacrylate Example 24Photolithography P-21 Dipentaerythritol PGMEA P1 C-9 J1 hexaacrylateExample 25 Photolithography P-22 Dipentaerythritol PGMEA P1 C-10 J1hexaacrylate Example 26 Photolithography P-23 Dipentaerythritol PGMEA P1C-4 J1 hexaacrylate Example 27 Photolithography P-24 DipentaerythritolPGMEA P1 C-13 J1 hexaacrylate Comparative Photolithography ComparativeDipentaerythritol PGMEA P1 C-9 J1 Example 1 compound-1 hexaacrylateComparative Photolithography Comparative Dipentaerythritol PGMEA P1 C-9J1 Example 2 compound-2 hexaacrylate Comparative PhotolithographyComparative Dipentaerythritol PGMEA P1 C-9 J1 Example 3 compound-3hexaacrylate

TABLE 6 PGMEA Change in spectrum Heat solvent Color between before andresistance solubility migration after development Example 1 B A B CExample 2 B A B C Example 3 B A A C Example 4 A A A AA Example 5 A A AAA Example 6 A A A AA Example 7 A A A AA Example 8 A A A AA Example 9 AA A AA Example 10 A A A AA Example 11 A A A AA Example 12 A A A AAExample 13 A A A AA Example 14 A A A AA Example 15 A A A AA Example 16 AA A AA Example 17 A A A AA Example 18 A A A AA Example 19 A A A AAExample 20 A A A AA Example 21 A A A AA Example 22 A A A AA Example 23 AA A AA Example 24 A A A AA Example 25 A A A AA Example 26 A A A AAExample 27 A A A AA Comparative C B C C Example 1 Comparative C B C CExample 2 Comparative C D C C Example 3

TABLE 7 Chain Epoxy Method for Dye Curable Photopoly- transfer Partscom- Parts Alkali- manufacturing compound compound Solvent Pigmentmerization agent by pound by soluble color filter (A) (B) (C) dispersioninitiator (S) mass (E) mass resin Example 28 Photolithography A-1Dipentaerythritol PGMEA/ P2 C-4 — — — — J1 hexaacrylate cyclo- hexanone= 50/50 (wt) Example 29 Photolithography A-2 Dipentaerythritol PGMEA/ P2C-5 — — — — J1 hexaacrylate cyclo- hexanone = 50/50 (wt) Example 30Photolithography A-14 Dipentaerythritol PGMEA P3 C-4 — — — — J1hexaacrylate Example 31 Photolithography P-1 Dipentaerythritol PGMEA/ P2C-9 — — — — J1 hexaacrylate cyclo- hexanone = 60/40 (wt) Example 32Photolithography P-2 Dipentaerythritol PGMEA P2 C-7 — — — — J1hexaacrylate Example 33 Photolithography P-3 Dipentaerythritol PGMEA P2C-13 — — — — J1 hexaacrylate Example 34 Photolithography P-4Dipentaerythritol PGMEA P2 C-9 — — — — J1 hexaacrylate Example 35Photolithography P-5 Dipentaerythritol PGMEA P2 C-10 — — — — J1hexaacrylate Example 36 Photolithography P-6 Dipentaerythritol PGMEA/ P2C-11 — — — — J1 hexaacrylate cyclo- pentanone = 70/30 (wt) Example 37Photolithography P-7 Dipentaerythritol PGMEA P4 C-12 — — — — J1hexaacrylate Example 38 Photolithography P-8 Dipentaerythritol PGMEA P2C-13 — — — — J1 hexaacrylate Example 39 Photolithography P-9Dipentaerythritol PGMEA P2 C-4 — — — — J1 hexaacrylate Example 40Photolithography P-10 Dipentaerythritol PGMEA P2 C-9 — — — — J1hexaacrylate Example 41 Photolithography P-11 Dipentaerythritol PGMEA/P2 C-5 — — — — J1 hexaacrylate cyclo- pentanone = 50/50 (wt) Example 42Photolithography P-12 Dipentaerythritol PGMEA P2/P4 = C-13 — — — — J1hexaacrylate 50/50 (wt) Example 43 Photolithography P-13Dipentaerythritol PGMEA P2 C-10 — — — — J1 hexaacrylate Example 44Photolithography P-14 Dipentaerythritol PGMEA P2 C-8 — — — — J2hexaacrylate Example 45 Photolithography P-15 Dipentaerythritol PGMEA P2C-6 — — — — J1 hexaacrylate Example 46 Photolithography P-16Dipentaerythritol PGMEA P2 C-11 — — — — J1 hexaacrylate Example 47Photolithography P-17 Dipentaerythritol PGMEA P2 C-9 — — — — J1hexaacrylate Example 48 Photolithography P-18 Dipentaerythritol PGMEA P2C-12 — — — — J1 hexaacrylate Example 49 Photolithography P-19Dipentaerythritol PGMEA P2 C-10 — — — — J1 hexaacrylate Example 50Photolithography P-20 Dipentaerythritol PGMEA P4 C-4 — — — — J1hexaacrylate Example 51 Photolithography P-21 Dipentaerythritol PGMEA P2C-9 — — — — J1 hexaacrylate Example 52 Photolithography P-22Dipentaerythritol PGMEA P2 C-10 — — — — J1 hexaacrylate Example 53Photolithography P-23 Dipentaerythritol PGMEA P2 C-4 — — — — J1hexaacrylate Example 54 Photolithography P-24 Dipentaerythritol PGMEAP2/P4 = C-13 — — — — J1 hexaacrylate 50/50 (wt) ComparativePhotolithography Comparative Dipentaerythritol PGMEA P2 C-9 — — — — J1Example 4 compound-1 hexaacrylate Comparative PhotolithographyComparative Dipentaerythritol PGMEA P2 C-9 — — — — J1 Example 5compound-2 hexaacrylate Comparative Photolithography ComparativeDipentaerythritol PGMEA P2 C-9 — — — — J1 Example 6 compound-3hexaacrylate

TABLE 8 Cyclohex- anone Change in spectrum Heat solvent Color betweenbefore and resistance solubility migration after development Example 28B A B C Example 29 B A B C Example 30 B A A C Example 31 A A A AAExample 32 A A A AA Example 33 A A A AA Example 34 A A A AA Example 35 AA A AA Example 36 A A A AA Example 37 A A A AA Example 38 A A A AAExample 39 A A A AA Example 40 A A A AA Example 41 A A A AA Example 42 AA A AA Example 43 A A A AA Example 44 A A A AA Example 45 A A A AAExample 46 A A A AA Example 47 A A A AA Example 48 A A A AA Example 49 AA A AA Example 50 A A A AA Example 51 A A A AA Example 52 A A A AAExample 53 A A A AA Example 54 A A A AA Comparative C B C C Example 4Comparative C B C C Example 5 Comparative C D C C Example 6

TABLE 9 Chain Epoxy Method for Dye Curable Photopoly- transfer Partscom- Parts Alkali- manufacturing compound compound Solvent Pigmentmerization agent by pound by soluble color filter (A) (B) (C) dispersioninitiator (S) mass (E) mass resin Example 55 Photolithography P-25A-DPH-12E PGMEA/ P2 C-9 S-1 0.02 — — J1 cyclo- hexanone = 50/50 (wt)Example 56 Photolithography P-26 A-DPH-12E PGMEA/ P2 C-9 S-2 0.02 — — J1cyclo- hexanone = 50/50 (wt) Example 57 Photolithography P-27 KAYARADPGMEA/ P2 C-4 S-3 0.01 — — J1 RP-1040 cyclo- hexanone = 60/40 (wt)Example 58 Photolithography P-28 A-DPH-12E PGMEA/ P2 C-9 S-4 0.01 — — J1cyclo- pentanone = 50/50 Example 59 Photolithography P-29 KAYARAD PGMEA/P2 C-5 S-5 0.01 — — J2 RP-1040 cyclo- hexanone = 50/50 (wt) Example 60Photolithography P-30 KAYARAD PGMEA/ P2 C-9 S-1 0.01 — — J1 RP-1040cyclo- hexanone = 50/50 (wt) Example 61 Photolithography P-31 A-DPH-12EPGMEA/ P4 C-9 — — — — J1 cyclo- hexanone = 50/50 (wt) Example 62Photolithography P-32 A-DPH-12E PGMEA/ P2 C-9 — — — — J1 cyclo-pentanone = 50/50 (wt) Example 63 Photolithography P-33 KAYARAD PGMEA/P2 C-9 — — — — J1 RP-1040 cyclo- pentanone = 50/50 Example 64Photolithography P-34 A-DPH-12E PGMEA/ P2 C-9 — — E1 0.3 J1 cyclo-hexanone = 50/50 (wt) Example 65 Photolithography P-35 A-DPH-12E PGMEA/P2 C-9 — — E1/E3 = 0.3 J2 cyclo- 1/1 hexanone = 50/50 (wt) Example 66Photolithography P-36 A-DPH-12E PGMEA/ P4 C-9 — — — — J1 cyclo- hexanone= 50/50 (wt) Example 67 Photolithography P-37 A-DPH-12E PGMEA/ P2 C-9 —— — — J1 cyclo- hexanone = 50/50 (wt) Example 68 Photolithography P-38KAYARAD PGMEA/ P2 C-9 — — — — J1 RP-1040 cyclo- hexanone = 50/50 (wt)Example 69 Photolithography P-38 A-DPH-12E PGMEA/ P2/P3 = C-9 — — — — J1cyclo- 50/50 (wt) hexanone = 50/50 (wt) Example 70 Photolithography P-39A-DPH-12E PGMEA/ P2 C-9 — — — — J1 cyclo- hexanone = 40/60 (wt) Example71 Photolithography P-31 A-DPH-12E PGMEA/ P2 C-9 — — — — J1 cyclo-hexanone = 50/50 (wt) Example 72 Photolithography P-32 A-DPH-12E PGMEA/P2 C-9 — — — — J2 cyclo- hexanone = 50/50 (wt) Example 73Photolithography P-31 KAYARAD PGMEA/ P2 C-9/C-5 = S-3 0.01 — — J1RP-1040 cyclo- 50-50 (wt) pentanone = 50/50 (wt) Example 74Photolithography P-32 A-DPH-12E PGMEA/ P2 C-9/C-5 = — — E2 0.3 J1 cyclo-50-50 (wt) pentanone = 50/50 (wt) Example 75 Photolithography P-27A-DPH-12E PGMEA/ P2 C-9 — — E2/E4 = 03 J1 cyclo- 1/1 hexanone = 50/50(wt) Example 76 Photolithography P-27 A-DPH-12E PGMEA/ P2 C-9 S-1 0.01 —— J2 cyclo- pentanone = 50/50 (wt) Example 77 Photolithography P-27A-DPH-12E PGMEA/ P2 C-9/C-5 = S-1 0.01 — — J1 cyclo- 50-50 (wt) hexanone= 50/50 (wt) Example 78 Photolithography P-40 KAYARAD PGMEA/ P2 C-9 — —— — J1 RP-1040 cyclo- hexanone = 50/50 (wt) Example 79 PhotolithographyP-41 KAYARAD PGMEA/ P2 C-9 — — — — J1 RP-1040 cyclo- hexanone = 50/50(wt) Example 80 Photolithography P-42 KAYARAD PGMEA/ P2 C-9 — — — — J1RP-1040 cyclo- hexanone = 50/50 (wt) Example 81 Photolithography P-29KAYARAD PGMEA/ P5 C-9 — — — — J1 RP-1040 cyclo- hexanone = 50/50 (wt)Example 82 Photolithography P-30 KAYARAD PGMEA/ P5 C-9 — — — — J1RP-1040 cyclo- hexanone = 50/50 (wt) Example 83 Dry etching A-40A-DPH-12E PGMEA/ P2 C-9 — — — — J1 cyclo- pentanone = 50/50 (wt) Example84 Dry etching A-41 Dipenta- PGMEA/ P2 C-9 — — — — J1 erythritol cyclo-hexa- pentanone = acrylate 50/50 (wt) Example 85 Dry etching A-42KAYARAD PGMEA/ P2 C-9 — — — — J1 RP-1040 cyclo- hexanone = 50/50 (wt)Example 86 Dry etching A-43 KAYARAD PGMEA/ P2 C-9 — — — — J1 RP-1040cyclo- hexanone = 50/50 (wt) Example 87 Dry etching P-40 KAYARAD PGMEA/P2 C-9 — — — — J1 RP-1040 cyclo- hexanone = 50/50 (wt) Example 88 Dryetching P-41 KAYARAD PGMEA/ P2 C-9 — — — — J1 RP-1040 cyclo- hexanone =50/50 (wt) Example 89 Dry etching P-42 KAYARAD PGMEA/ P2 C-9 — — — — J1RP-1040 cyclo- hexanone = 50/50 (wt) Example 90 Dry etching P-43Dipenta- PGMEA/ P2 C-9 — — — — J1 erythritol cyclo- hexa- hexanone =acrylate 50/50 (wt) Example 91 Dry etching P-44 Dipenta- PGMEA/ P2 C-9 —— — — J1 erythritol cyclo- hexa- hexanone = acrylate 50/50 (wt) Example92 Dry etching P-27 A-DPH-12E PGMEA/ P2 C-9 — — — — J1 cyclo- hexanone =50/50 (wt) Example 93 Dry etching P-31 A-DPH-12E PGMEA/ P2 C-9 — — — —J1 cyclo- hexanone = 50/50 (wt)

TABLE 10 Cyclohex- anone Change in spectrum Heat solvent Color betweenbefore and resistance solubility migration after development Example 55A A A AA Example 56 A A A AA Example 57 A A A AA Example 58 A A A AAExample 59 A A A AA Example 60 A A A AA Example 61 A A A AA Example 62 AA A AA Example 63 A A A AA Example 64 A A A AA Example 65 A A A AAExample 66 A A A AA Example 67 A A A AA Example 68 A A A AA Example 69 AA A AA Example 70 A A A AA Example 71 A A A AA Example 72 A A A AAExample 73 A A A AA Example 74 A A A AA Example 75 A A A AA Example 76 AA A AA Example 77 A A A AA Example 78 A A A AA Example 79 A A A AAExample 80 A A A AA Example 81 A A A AA Example 82 A A A AA Example 83 BA B C Example 84 B A B C Example 85 B A B C Example 86 B A B C Example87 A A A AA Example 88 A A A AA Example 89 A A A AA Example 90 A A A AAExample 91 A A A AA Example 92 A A A AA Example 93 A A A AA

It could be seen that in the case where a color filter is manufacturedusing the compositions of Examples, the heat resistance is excellent.Further, it could also be seen that the compositions of Examples haveexcellent solvent resistance and color migration, and small change inspectrum between before and after development, whereas the compositionsof Comparative Examples have deterioration in those properties.

What is claimed is:
 1. A xanthene dye represented by General Formula(A5):

in General Formula (A5), R²⁰ to R²³ each independently represent ahydrogen atom, an aliphatic hydrocarbon group, or an aromatichydrocarbon group; and A represents an anionic moiety represented by anyone of the following General Formula (AN-1) to (AN-4)):

in General Formula (AN-1), * represents a bonding site to a xanthenestructure; and Rf₁ represents an aliphatic hydrocarbon group, ahalogenated aliphatic hydrocarbon group, an aromatic hydrocarbon group,or a halogenated aromatic hydrocarbon group; in General Formula(AN-2), * represents a bonding site to a xanthene structure; and Rf₂represents a halogenated aliphatic hydrocarbon group; in General Formula(AN-3), * represents a bonding site to a xanthene structure; Rf₃represents an aliphatic hydrocarbon group, a halogenated aliphatichydrocarbon group, an aromatic hydrocarbon group, or a halogenatedaromatic hydrocarbon group; and B represents a substituent; and inGeneral Formula (AN-4), * represents a bonding site to a xanthenestructure; Rf₄ represents a halogenated aliphatic hydrocarbon group; andB represents a substituent.
 2. The xanthene dye according to claim 1,wherein A in General Formula (A5) represents an anionic moietyrepresented by any one of the General Formula (AN-1) and (AN-2).
 3. Thexanthene dye according to claim 1, wherein A in General Formula (A5)represents an anionic moiety represented by the General Formula (AN-1).4. The xanthene dye according to claim 1, wherein A in General Formula(A5) represents an anionic moiety represented by the General Formula(AN-2).
 5. The xanthene dye according to claim 1, wherein R²⁰ in GeneralFormula (A5) represents a hydrogen atom or an aliphatic hydrocarbongroup having 1 to 6 carbon atoms.
 6. The xanthene dye according to claim1, wherein R²⁰ in General Formula (A5) represents a hydrogen atom or analiphatic hydrocarbon group having 1 to 6 carbon atoms.
 7. The xanthenedye according to claim 1, wherein R²¹ in General Formula (A5) representsan aliphatic hydrocarbon group having 1 to 6 carbon atoms, or anaromatic hydrocarbon group having 6 to 15 carbon atoms.
 8. The xanthenedye according to claim 1, wherein R²³ in General Formula (A5) representsan aliphatic hydrocarbon group having 1 to 6 carbon atoms, or anaromatic hydrocarbon group having 6 to 15 carbon atoms.
 9. The xanthenedye according to claim 1, wherein Rf₁ in General Formula (AN-1)represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, ahalogenated aliphatic hydrocarbon group having 1 to 6 carbon atoms, anaromatic hydrocarbon group having 6 to 12 carbon atoms, or a halogenatedaromatic hydrocarbon group having 6 to 12 carbon atoms.
 10. The xanthenedye according to claim 1, wherein Rf₂ in General Formula (AN-2)represents a halogenated aromatic hydrocarbon group having 6 to 12carbon atoms.
 11. The xanthene dye according to claim 1, wherein Rf₃ inGeneral Formula (AN-3) represents an aliphatic hydrocarbon group having1 to 6 carbon atoms, a halogenated aliphatic hydrocarbon group having 1to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbonatoms, or a halogenated aromatic hydrocarbon group having 6 to 12 carbonatoms.
 12. The xanthene dye according to claim 1, wherein Rf₄ in GeneralFormula (AN-3) represents a halogenated aliphatic hydrocarbon grouphaving 1 to 6 carbon atoms.
 13. The xanthene dye according to claim 1,wherein B in General Formula (AN-3) represents a substituent whichcontains a crosslinkable group.
 14. The xanthene dye according to claim1, wherein Rf₄ in General Formula (AN-4) represents a halogenatedaromatic hydrocarbon group having 6 to 12 carbon atoms.
 15. The xanthenedye according to claim 1, wherein B in General Formula (AN-3) representsa substituent which contains a crosslinkable group.
 16. The xanthene dyeaccording to claim 1, wherein B in General Formula (AN-4) represents asubstituent which contains a crosslinkable group.
 17. The xanthene dyeaccording to claim 1, wherein B in General Formula (AN-3) is a groupformed by combination of a crosslinkable group and a linking group. 18.The xanthene dye according to claim 1, wherein B in General Formula(AN-4) is a group formed by combination of a crosslinkable group and alinking group.
 19. The xanthene dye according to claim 1, wherein B inGeneral Formula (AN-3) is a group formed by combination of acrosslinkable group and at least one linking group selected from analkylene group having 1 to 6 carbon atoms, an arylene group having 6 to12 carbon atoms, —O—, —S—, —CO—, —SO—, —SO₂—, and —NR—, wherein R in—NR— is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.20. The xanthene dye according to claim 1, wherein B in General Formula(AN-4) is a group formed by combination of a crosslinkable group and atleast one linking group selected from an alkylene group having 1 to 6carbon atoms, an arylene group having 6 to 12 carbon atoms, —O—, —S—,—CO—, —SO—, —SO₂—, and —NR—, wherein R in —NR— is a hydrogen atom or analkyl group having 1 to 3 carbon atoms.